Electrical and photoluminescence properties of Sm3+ doped Na0.5La0.5Bi8-xSmxTi7O27 ceramics

In this study, Sm³⁺ doped Na_0.5La_0.5Bi_8-xSm_xTi₇O₂₇ (NBT-BITL-xSm, x = 0, 0.01, 0.015, 0.02, and 0.03) ceramics were synthesized via a conventional solid-state reaction process. The structural, electrical, and photoluminescence properties of NBT-BITL-xSm ceramics were systematically investigated. The crystal structure of NBT-BITL-xSm was refined using XRD Rietveld refinement and found to possess a single orthorhombic structure at room temperature. Raman spectroscopy revealed that Sm³⁺ ions preferred to substitute for Bi³⁺ located in the A-sites of pseudo-perovskite layers, inducing a slight decrease in orthorhombic distortion. Strong characteristic emission peaks of Sm³⁺ ions were observed in orange-red regions under a 407 nm laser source, and the sample with x = 0.015 achieved the optimal photoluminescent property. Dielectric measurements showed double anomaly permittivity peaks at the temperature of 589 and 600^°C (T_m and T_c, respectively). The complex impedance spectrum indicated that the electrical conductivities mainly originated from crystal grains at high temperature. The activation energy was calculated to be 1.37–1.44 eV from Arrhenius fitting results. After Sm³⁺ substitution, the activation energy for conductivity was increased as a result of reduced oxygen vacancies.     

Energy transfer and photoluminescent analysis of a novel color-tunable Ba2Y1-xV3O11:xSm3+ nanophosphor for single-phased phosphor-converted white LEDs

Metal nitrates are used to synthesize a series of novel Ba₂Y_1-xV₃O₁₁:xSm³⁺ nanophosphors via urea-assisted solution combustion route. X-ray diffraction (XRD), diffuse reflectance (DR), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy were employed to analyse the structure, morphology, photoluminescent behaviour and energy transfer mechanism. Rietveld analysis over Ba₂Y_0.98Sm_0.02V₃O₁₁ showed that Y³⁺ ions can be well-replaced by trivalent samarium ions without resulting any major alteration in the crystal structure of host lattice. Furthermore, the lattice parameters were determined for both the host as well as the doped composition. The Scherrer equation yielded an average particle size of 44?nm, which in turn was further confirmed by TEM micrographs. The optical band-gap of the host (3.92?eV) was calculated from the diffuse reflectance spectra. Moreover, the photoluminescence spectral studies showed that under near ultra-violet (NUV) excitation of 340?nm, our nanophosphor powder exhibits the characteristic emission peaks of trivalent samarium along with the emission of VO₄^3? (501?nm) group. The excitation energy transfer from vanadate group to Sm³⁺ produced a systematic color tunablity in white region itself. The optimum Sm³⁺ concentration for better luminescence was found to be 2?mol%. The critical distance for energy transfer was calculated to be 29.02?Å, which in turn assisted to shortlist the mechanism responsible for luminescence-quenching (dipole-dipole) arising from the over-doping of the activator. The photoluminescence decay curves revealed the decay kinetics of ⁴G_5/2 electronic state. Finally, the calculation of CIE color coordinates from emission spectra in MATLAB program unveiled a somewhat white-light emitter which may find potential applications in phosphor-converted white light emitting diodes (PC-WLED) under near-ultraviolet (NUV) excitation.     

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.     

Dielectric,ferroelectric, and photoluminescent properties of Sm-doped Bi4Ti3O12 thin films synthesized by sol-gel method

We report on the structure, dielectric, ferroelectric, and photoluminescent properties of Sm³⁺-doped Bi₄Ti₃O₁₂ thin films which were prepared on fused silica and Pt/Ti/SiO₂/Si substrates by sol-gel method. The X-ray diffraction analysis confirmed that the Bi_4-xSm_xTi₃O₁₂ (BSmT) thin films were well crystallized in layered perovskite structure without any secondary phase. Raman spectra indicated that the structure of BSmT thin films was significantly distorted because of the Sm³⁺ doping. An appropriate doping amount of Sm³⁺ ions leads to obvious enhancement in ferroelectric and dielectric properties of BSmT thin films due to structure distortion and reduction in defects. In addition, the BSmT thin films also show orange-red color emission at 601?nm and long florescence lifetime (> 0.6?ms). This study indicated that lead-free BSmT thin films, which are featuring good electrical and photoluminescent properties, may have potential applications in integrated optoelectronic devices.     

Synthesis and spectroscopic analysis of Sm3+ doped CeO2 ceramic powders for the application of white LEDs

Orange-red light-emitting Sm³⁺-doped cerium oxide (CeO₂) ceramic powder with various concentrations of Sm³⁺ ions was prepared through a sol-gel process. X-ray diffraction and Rietveld analysis confirmed the formation of a purely cubic structure with a space group of $\mathit{Fm}\stackrel{?}{3}m$. The lattice parameters and unit cell volumes of the CeO₂:Sm³⁺ powder increased with the concentration of Sm³⁺ ions. The energy-dispersive X-ray spectra and corresponding mapping images confirmed the elemental composition and adequate dispersion of all elements in the CeO₂:Sm³⁺ powder. A broad excitation band at approximately 365?nm was observed in the excitation spectra of CeO₂:Sm³⁺ phosphors owing to the charge transfer transition from O 2p to Ce 4f orbitals. The Sm³⁺ doped CeO₂ phosphors emitted sharp luminescence with a main peak at 615?nm under excitation at 360?nm. The spectral analysis revealed that the CeO₂:Sm³⁺ phosphors exhibited strong orange-red emission. Concentration quenching was observed in the CeO₂:Sm³⁺ phosphors with 0.5?mol% of critical concentration of Sm³⁺ ions due to dipole dipole interaction of two nearest Sm³⁺ ions. The quantum efficiency was observed as high as 58%. The thermal stability of the present materials was estimated with the evaluation of activation energy as 0.31?eV. The broad excitation band and sharp orange–red emission indicated the potential use of CeO₂:Sm³⁺ phosphors for white light-emitting diodes.     

Dazzling cool white light emission from Ce3+/Sm3+ activated LBZ glasses for W-LED applications

We synthesized a batch of co-doped (Ce³⁺+Sm³⁺): LBZ glass specimens by melt quenching process and their structural and radiation properties were studied by employing XRD, FE-SEM, optical absorption, photoluminescence and lifetime measurements. UV–Vis–NIR absorption studies of the co-doped (Ce³⁺+Sm³⁺): LBZ glassy matrix displays pertinent bands of both Ce³⁺ and Sm³⁺ ions. Individually doped Sm³⁺: LBZ glass exhibit bright orange emission at 603?nm (⁴G_5/2 → ⁶H_7/2) under the excitation of 403?nm. Nevertheless, the luminescence intensities pertaining to Sm³⁺ were extraordinarily increased by co-doping with Ce³⁺ ions to Sm³⁺: LBZ glassy matrices because of energy transfer from Ce³⁺ to Sm³⁺. The fluorescence spectra of co-doped (Ce³⁺+Sm³⁺): LBZ exhibits characteristic emission bands of Ce³⁺ (441?nm, blue) and Sm³⁺ (603?nm, reddish orange) under the excitation of 362?nm. Decay curves of Ce³⁺ and Sm³⁺ ions in co-doped glass has been fitted to double exponential nature. The decreasing lifetime of donor ion and rising lifetime of acceptor ion in double doped glass could support the energy transfer from Ce³⁺ to Sm³⁺ ions in the host matrix. The CIE coordinates and CCT values were calculated for all the obtained co-doped glassy samples from their luminescence spectra. By adding Ce³⁺ ions to individually doped Sm³⁺: LBZ glass matrix, the emitting color changes from reddish orange to white light which resembles the energy transfer from Ce³⁺ to Sm³⁺ ions. These studies, perhaps implied that attained co-doped (Ce³⁺+Sm³⁺): LBZ glassy samples are potential materials for white lighting appliances.     

LiCa3MgV3O12:Sm3+: A new high-efficiency white-emitting phosphor

A novel single-phased white-light-emitting phosphor Sm³⁺ doped LiCa₃MgV₃O₁₂ (LCMV) was developed. The LCMV host was one self-activated bluish-green emitting phosphor, which possessed an efficient excitation band in the 250–400?nm wavelength range and showed an intense broadband bluish-green emission with internal quantum efficiency (IQE) of 39%. Doping Sm³⁺ ions in to LCMV host induced tunable-color emissions, due to the energy transfer from [VO₄]^3? to Sm³⁺ ions. Importantly, under 340?nm excitation, the LCMV:Sm³⁺ can emitted bright white light by combining the self-activated luminescence of LCMV host and the red emissions of Sm³⁺ ions, and the IQE of the white-emitting composition-optimized LCMV:0.01Sm³⁺ phosphors reached up to 45%. These white-emitting LCMV:Sm³⁺ phosphors have potential applications in white light-emitting diodes and optical display devices.     

Sol-gel synthesis and luminescence properties of Ba2SiO4:Sm3+ nanostructured phosphors

Ba₂SiO₄:Sm³⁺ nanostructure phosphors have been synthesized by a simple sol-gel method. Phase evaluation, structural characteristics and photoluminescence properties of the synthesized Ba₂SiO₄:Sm³⁺ powders were studied using field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA), Fourier transform infrared spectroscopy (FTIR), and photoluminescence spectroscopy (PL). X-ray diffraction results showed that all synthesized samples were single-phase barium silicate (Ba₂SiO₄) and samarium (Sm) ions were incorporated into the lattice of Ba₂SiO₄. Adding samarium to barium silicate changed the microstructure from vermicular to spherical structures. The Photoluminescence spectrum of Ba₂SiO₄:Sm³⁺ phosphors exhibited characteristic emission peaks at 562?nm which is due to the ⁴G_{5/2 →}⁶H_7/2 transition of samarium ions and corresponds to the orange region. The results showed that the barium silicate activated with 0.08?mol samarium exhibited the highest PL intensity.     

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.     

Cathodoluminescence and thermoluminescence of ZnB2O4:Eu3+ phosphors prepared via wet-chemical synthesis

In present work, a series of Eu doped zinc borate, ZnB₂O₄, phosphors prepared via wet chemical synthesis and their structural, surface morphology, cathodoluminescence (CL) and thermoluminescence (TL) properties have been studied. Phase purity and crystal structure of as-prepared samples are confirmed by X-ray diffraction measurements (XRD) and they were well consistent with PDF card No. 39-1126, indicating the formation of pure phase. The thermoluminescence (TL) behaviors of Eu activated ZnB₂O₄ host lattice are studied for various beta doses ranging from 0.1 to 10?Gy. The high-temperature peak of Eu activated sample located at 192?°C exhibited a linear dose response in the range of 0.1–10?Gy. Initial rise (IR) and peak shape (PS) methods were used to determine the activation energies of the trapping centres. The effects of the variable heating rate on TL behaviour of Eu activated ZnB₂O₄ were also studied. When excited using an electron beam induced light emission (i.e cathodoluminescence, CL) at room temperature (RT), the as-prepared phosphors generate reddish-orange color due to predominant emission peaks of Eu³⁺ ions located at 576–710?nm assigned to the ⁵D₀→⁷F_J (J=1,2,3, and 4) transitions. The maximum CL intensity for Eu³⁺ ions at 614?nm with transition ⁵D₀→⁷F₂ was reached Eu³⁺ concentration of 5?mol%; quenching occurred at higher concentrations. Strong emission peak for Eu³⁺ ions at 614?nm with transition ⁵D₀→⁷F₂ is observed. The CL experimental data indicate that ZnB₂O₄:Eu³⁺ phosphor as an orange-red emitting phosphor may be promising luminescence materials for the optoelectronic applications.     

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.     

Photoluminescence properties of a double perovskite tungstate based red-emitting phosphor NaLaMgWO6:Sm3+

In this work, the conventional solid-state method was applied to synthesize a series of red-emitting NaLaMgWO₆:Sm³⁺ phosphors. The crystal structure, phase purity, morphology, particle size distribution as well as elemental composition of the as-prepared phosphors were investigated carefully with the aid of XRD, SEM, EDS, FT-IR analyses, indicating the high-purity and micron-sized NaLaMgWO₆:Sm³⁺ phosphors with monoclinic structure were prepared successfully. The spectroscopic properties of Sm³⁺ in NaLaMgWO₆ host including UV–vis diffuse reflection spectrum, photoluminescence excitation and emission spectra, decay curves, chromaticity coordinates and internal quantum efficiency were investigated in detail. Upon excitation with UV (290 nm) and n-UV (406 nm), NaLaMgWO₆:Sm³⁺ phosphor presented red emission corresponding to the ⁴G_5/2→⁶H_J (J = 5/2, 7/2, 9/2, and 11/2) transitions of Sm³⁺, in which the hypersensitive electronic dipole transition ⁴G_5/2→⁶H_9/2 (645 nm) was with the strongest emission intensity because Sm³⁺ ions were located at a lattice site with anti-inversion symmetry. The optimal concentration of Sm³⁺ was different for the given excitation wavelength such as 290 nm and 406 nm, which was interpreted by the extra effect of the energy transfer from W⁶⁺-O^2- group to Sm³⁺. The decay lifetime for ⁴G_5/2→⁶H_9/2 transition of Sm³⁺ was very short (< 1 ms) and decreased with the increasing Sm³⁺ concentration. The present investigation indicates that NaLaMgWO₆:Sm³⁺ phosphor could be a potential red component for application in w-LEDs.     

Effect of Y3+-O2- partial substitution with Ca2+-F- on the luminescence enhancement of Y2Mo3O12:Sm3+ red-emitting phosphors

To improve the luminescence property of Sm³⁺ in Y₂Mo₃O₁₂, partial Ca²⁺-F^- co-substituted Y₂Mo₃O₁₂:Sm³⁺ phosphor, namely Y_2-xCa_xMo₃O_12-xF_x:Sm³⁺, was prepared using a solid-state method. The effect of introducing Ca²⁺-F^- ion pairs on structure and luminescence properties of Y₂Mo₃O₁₂:Sm³⁺ was studied in depth. XRD patterns not only manifested that all as-prepared Y_2-xCa_xMo₃O_12-xF_x:Sm³⁺ samples had standard Y₂Mo₃O₁₂ structure, but also indicated the introduction of Ca²⁺-F^- ion pairs did not cause the change of crystal structure. Under the near ultraviolet excitation of 404 nm, the emission peaks of Y₂Mo₃O₁₂:Sm³⁺ were located at 567 nm, 605 nm and 652 nm, respectively, resulting from the 4f→4f electron transitions of Sm³⁺ ions. Furthermore, the luminescence intensity of Sm³⁺ was obviously enhanced through the co-substitution of Y³⁺-O^2- ions with Ca²⁺-F^- ions in Y₂Mo₃O₁₂ structure, and the chromaticity coordinates moved towards red region, which due to the environmental effect of crystal field around Sm³⁺. Besides, the red LED device was manufactured for suitable chromaticity parameters. All results indicated that the as-prepared Y_1.84Ca_0.06Mo₃O_11.94F_0.06:0.10Sm³⁺ red-emitting phosphor could become a promising candidate for application of white light-emitting diodes and plant illumination.     

Color-tunable up-conversion luminescence of Zn(AlxGa1-x)2O4:Yb3+,Tm3+,Er3+ powders

Color-tunable up-conversion powder phosphors Zn(Al_xGa_1-x)₂O₄: Yb³⁺,Tm³⁺,Er³⁺ were synthesized via high temperature solid-state reaction. Also, the morphological and structural characterization, up-conversion luminescent properties were all investigated in this paper. In brief, under the excitation of a 980?nm laser, all powders have same emission peaks containing blue emission at 477?nm (attributed to ¹G₄→³H₆ transition of Tm³⁺ ions), green emission at 526?nm and 549?nm (attributed to ²H_11/2→ ⁴I_15/2 and ⁴S_3/2→⁴I_15/2 transition of Er³⁺ ions respectively), red emission at about 659?nm and 694?nm (attributed to ⁴F_9/2→⁴I_15/2 transition of Er³⁺ ions and ³F₃→³H₆ transition of Tm³⁺ ions, respectively), which are not changed after the doping of Al³⁺ ions. However, the doping of Al³⁺ ions can enhance the up-conversion luminescent intensity and efficiency, while the emission color of as-prepared powder phosphors can be tunable by controlling the doping amount of Al³⁺ ions. Taking Zn(Al_0.5Ga_0.5)₂O₄:Yb,Tm,Er as the cut-off value, the emissions have clear blue-shift firstly and then show obvious red-shift with the increasing doping of Al³⁺ ions. Stated thus, pink emission in ZnAl₂O₄:Yb,Tm,Er, purplish pink emission in ZnGa₂O₄:Yb,Tm,Er and Zn(Al_0.9Ga_0.1)₂O₄:Yb,Tm,Er, purple emission in Zn(Al_0.1Ga_0.9)₂O₄:Yb,Tm,Er and Zn(Al_0.3Ga_0.7)₂O₄:Yb,Tm,Er, purplish blue emission in Zn(Al_0.7Ga_0.3)₂O₄:Yb,Tm,Er, blue emission in Zn(Al_0.5Ga_0.5)₂O₄:Yb,Tm,Er can be observed, which confirm the potential applications of as-prepared Zn(Al_xGa_1-x)₂O₄:Yb³⁺,Tm³⁺,Er³⁺ powder phosphors in luminous paint, infrared detection and so on.     

Potential red-emitting NaGd(MO4)2:R (M=W,Mo, R=Eu,Sm, Bi) phosphors for white light emitting diodes applications

NaGd(MO₄)₂:R (M=W, Mo, R=Eu³⁺, Sm³⁺, Bi³⁺) phosphors were synthesized by solid-state reaction. The structure and photoluminescence properties of the samples were characterized using X-ray powder diffraction and fluorescence spectrophotometry. The ⁵D₀→⁷F₂ transition of Eu³⁺, which led to a red emission of the phosphors, was dominantly observed in the photoluminescence spectra. The doped Bi³⁺ and Sm³⁺ efficiently sensitized the emission of Eu³⁺ and effectively extended and strengthened the absorption of near-UV light with wavelengths ranging from 395 to 405 nm. In addition, energy transfers from Bi³⁺ to Eu³⁺ and from Sm³⁺ to Eu³⁺ occurred. The chromaticity coordinates of the obtained phosphors were close to the standard values of the National Television Standard Committee (x=0.670, y=0.330). The results suggest that NaGd(WO₄)_2−y(MoO₄)_y:Eu³⁺, Sm³⁺, Bi³⁺ is an efficient red-emitting phosphor for light-emitting diode applications.     

Synthesis and photoluminescence properties of La1−xAlO3:xTb green phosphors for white LEDs

Tb³⁺-doped La_1−xAlO₃ phosphor powders are successfully synthesized by the solution combustion method, using citric acid as the combustion fuel. The crystal structure and photoluminescence properties of La_1−xAlO₃:xTb³⁺ phosphors are studied, depending on Tb³⁺ content. The strongest emission peak is found at 543 nm, which originates from the ⁵D₄→⁷F₅ transition of Tb³⁺ ions, indicating green emission. Among the fabricated phosphors, the La_0.9AlO₃:0.1Tb³⁺ phosphor emits the strongest green light. The excellent luminescent properties make it a possible candidate for white light-emitting diodes and various photonic applications.     

Synthesis,structure and luminescent properties of Eu3+ doped Ca3LiMgV3O12 color-tunable phosphor

A new vanadate Ca₃LiMgV₃O₁₂ and its Eu³⁺-doped counterparts were synthesized. Rietveld confinement result of Ca₃LiMgV₃O₁₂ host indicates that it belongs to cubic space group Ia-3d with parameters of a =?12.4300?Å, V =?1920.49?ų, Z?=?8. Under UV excitation, pure Ca₃LiMgV₃O₁₂ exhibits a bluish-green broadband emission at 490?nm, while Eu³⁺ doped Ca₃LiMgV₃O₁₂ shows one bluish-green broad band with a series of red sharp peaks, which originate from the V⁵⁺-O^2- charge transfer and the Eu³⁺ intra-4f transitions, respectively. The occurrence of VO₄→Eu³⁺ energy transfer is confirmed by decay lifetime analysis and time-resolved emission spectra. It is found that emitting color varies from bluish-green to orange-red with increasing Eu³⁺ concentration. VO₄ bluish-green and Eu³⁺ red emission shows different thermal quenching response with increasing temperature, due to their different activation energy.     

Effects of argon sintering atmosphere on luminescence characteristics of Ca6BaP4O17:Sm3+ phosphors

In this paper, Ca₆BaP₄O₁₇:Sm³⁺ and Li⁺ co-doped Ca₆BaP₄O₁₇:Sm³⁺ phosphors were synthesized in air and argon atmospheres using a solid-state reaction method. The phosphor morphologies and crystal structure were studied using scanning electron microscopy and X-ray diffraction, respectively. The emission and absorption characteristics were investigated using photoluminescence emission spectroscopy and diffuse reflectance spectroscopy. The surface states and composition of phosphor were investigated using X-ray photoelectron spectroscopy. The emission integrated intensities of the phosphors sintered in an argon atmosphere increased 3.5 fold than the ones sintered in air atmosphere, with Li⁺ ions becoming embedded in the lattice of the Ca₆BaP₄O₁₇:Sm³⁺ phosphor. This occurs because there are fewer defect/oxygen vacancies and less of the secondary phase forms, leading to better Sm³⁺ emission. The results suggest that sintering a mixture of the raw materials of a phosphor in an argon atmosphere is a good approach for synthesizing Ca₆BaP₄O₁₇:Sm³⁺ phosphor powders. The color purity and CIE values of an optimized phosphor sample sintered in an argon atmosphere with an Li⁺ ion compensator were calculated to be ~ 99.6% and (0.612,0.386) in the orange–red region under 405-nm excitation, respectively. Moreover, the solid solubility of Sm³⁺ ions in the Ca₆BaP₄O₁₇ host can be enhanced by using an argon atmosphere in the synthesis process.     

Tuning of Bi3+-related excitation and emission positions through crystal field modulation in the perovskite-structured La2(Znx, Mg1-x)TiO6 (0 ≤ x ≤ 1):Bi3+ solid solution for white LEDs

In the past year, emission-tunable crystals based on the rare-earth (RE) ions as luminescent center have been frequently reported for use in UV and blue converted white LEDs, but so far tuning the non-RE Bi³⁺ related emissions through the crystal field modulation is still not discovered in the perovskite crystals. In this work, we design and report a type of Bi³⁺ doped La₂(Zn_x,Mg_1-x)TiO₆ (0 ≤ x ≤ 1) perovskite solid solutions, which enable showing the tunable Bi³⁺ excitation and emission positions. The XRD results show that gradual substitution of smaller Mg²⁺ ions with larger Zn²⁺ ions can lead to the blue-shifting of X-ray diffraction (XRD) position, revealing the expansion of cell lattice. Together with structural analysis, our refined XRD and time-resolved spectral results reveal that there is only one type of La site available for Bi³⁺ substitution. With this regular crystal lattice change, the crystal field strength around Bi³⁺ ions is found to vary regularly, allowing to realization of the excitation and emission spectral tuning, i.e., the Bi³⁺ excitation and emission positions as the Mg ions are replaced by the Zn ions can tune from 348?nm to 392?nm and from 405?nm to 433?nm, respectively. This Bi³⁺ spectral tuning peak after calculated by the dielectric chemical bond theory features a linear relationship with the crystal field strength and, thus, is ascribed to the crystal field modulation. On basis of the La₂(Zn_0.4,Mg_0.6)TiO₆ blue, SrGa₂S₄:Eu²⁺ green and Y₂O₃:Eu³⁺ red phosphors, a UV converted warm white LED device with desirable color rendering index (CRI) of 78, correlated color temperature (CCT) of 3650 K and good luminous efficacy of 118.13?lm/W, is fabricated. This work provides new insights into using the crystal-field modulation to discover more Bi³⁺ emission-tunable crystals for white LEDs in the future.     

High-temperature thermoelectric properties of Sm3+-doped Ca3Co4O9+δ fabricated by spark plasma sintering

Ca_3-xSm_xCo₄O_9+δ (0 ≤ x ≤ 0.3) samples were fabricated by the sol-gel method followed by spark plasma sintering in vacuum. The high-temperature thermoelectric properties of the Ca_3-xSm_xCo₄O_9+δ were also studied, with an emphasis placed on the partial substitution of Sm³⁺ for Ca²⁺. The sintered Ca_3-xSm_xCo₄O_9+δ formed a monoclinic Ca₃Co₄O₉ phase and exhibited fine lamellar grains and dense morphology. With increased Sm³⁺ content, the electrical and thermal conductivities decreased, whereas the Seebeck coefficient significantly increased. Of the prepared samples, Ca_2.7Sm_0.3Co₄O_9+δ had the largest dimensionless figure-of-merit (0.175) at 800 °C. The results showed that the partial substitution of Sm³⁺ for Ca²⁺ in Ca₃Co₄O_9+δ is effective for enhancing its thermoelectric properties.