Soluble silica assisted synthesis and luminescent characteristics of yellow emitting CaSrSiO4:Eu2+ phosphors for warm white light production

To meet the challenges and additional requirements towards the development of white LED׳s with utmost efficacy, a sol–gel approach is adopted wherein a water soluble silicon compound is used as a silica source. The phosphor material obtained is subjected to detailed structural, morphological and luminescent studies. The results obtained show that the XRD patterns of Eu²⁺ doped CaSrSiO₄ phosphors are in good agreement with the CaSrSiO₄ (ICSD no. 49660) whose structure is orthorhombic. The output of the luminescence studies clearly portrays a broad yellow emission between 450 and 750 nm with a peak at ~600 nm under the broad excitation range. This confirms its efficient emission towards the development of a warm white light using blue LEDs. A red shift in the peak emission wavelength was observed for the prepared samples. This longer shift in wavelength can be credited to the sol–gel method adopted and is not offered by the conventional solid state reaction method. A warm white emitting LED was fabricated by combining near ultraviolet LED (400 nm) chip with our sol–gel synthesized CaSrSiO₄:Eu²⁺ phosphor. The CIE chromaticity coordinates (0.44 and 0.41), color correlated temperature (CCT) <4000 K, color rendering index (CRI) >80 provide their emission potentiality in the warm white light region.     

Tunable single-phased white-emitting Sr3Y(PO4)3:Dy3+ phosphors for near-ultraviolet white light-emitting diodes

Single-component white-emitting Sr₃Y(PO₄)₃:Dy³⁺ phosphors were synthesized by a high-energy deformation process. X-ray diffraction patterns showed the resulting crystallized phase to be of cubic structure, space group I-43d (no. 220). The broad-band excitation spectra between 250 and 500 nm were observed by monitoring the emission wavelength at 576 nm, which matches well with commercial near-UV or blue LED chips. Under a 352 nm excitation, the emission peaks were observed at 483 nm (blue), 576 nm (yellow), and 666 nm (red), corresponding to the ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2, and ⁴F_9/2 → ⁶H_11/2 transitions of Dy³⁺ ions. The optimized doping concentration of Dy³⁺ ion was 8 mol%. By controlling the Dy³⁺ ion concentration, tunable colors from white to yellow were obtained in Sr₃Y(PO₄)₃:Dy³⁺ phosphors. These results reveal that studied materials may be a promising candidate for white LED applications.     

Effect of Y doping on transport properties of La0.8Sr0.2MnO3 polycrystalline ceramics

In this study, La_0.8-xY_xSr_0.2MnO₃ (LYSMO) polycrystalline ceramics were prepared by means of sol-gel technique using methanol as solvent. X-ray diffraction (XRD) showed all samples to possess standard perovskite structure. Scanning electron microscopy (SEM) revealed samples with high compactness and grain size from 27.80 to 29.73 μm. Resistivity–temperature tests indicated sharp metal-insulator transition behavior of all samples accompanied by rapid transformation from ferromagnetism to paramagnetism (FM-PM). As Y³⁺ doping amounts rose, radius of A-site ions decreased, metal-insulator transition temperature (T_p) of polycrystalline samples shifted to lower temperatures, and resistivity increased. Temperature coefficient of resistance (TCR) and magnetoresistance (MR) were affected by introduction of Y³⁺. At x = 0.06, peak TCR and peak MR reached 4.85% K⁻¹ and 52.34%, respectively. Using double exchange (DE) interaction mechanism, electric transport performances of as-prepared ceramics were explained. These findings look promising for future applications of LYSMO materials in magnetic devices and infrared detectors.     

Photoluminescence and energy transfer of Lu3Al5O12:Ce3+, Pr3+ phosphors

Ce³⁺ and Pr³⁺ co?doped Lu₃Al₅O₁₂ phosphors were synthesized by the sol–gel process, and their crystal structure, photoluminescence (PL) properties, and energy transfer (ET) from the Ce³⁺ to Pr³⁺ were studied. The Lu_2.94?yAl₅O₁₂:0.06Ce³⁺, yPr³⁺ phosphors (0.002 ≤ y ≤ 0.008) showed the green?yellow emission from the ²D_3/2 → ²F_{5/2, 7/2} transition of Ce³⁺ and the red emission at 610 and 637 nm, which were caused by the ¹D₂→³H₄ and ³P₀→³H₅ transitions of Pr³⁺, respectively. The optimal concentration of Pr³⁺ for efficient ET was found to be x = 0.006. The electric quadrupole?quadrupole interaction was responsible for the concentration quenching in the Lu_2.94?yAl₅O₁₂:0.06Ce³⁺, yPr³⁺ phosphors, based on Dexter's theory. The incorporation of Pr³⁺ for Lu³⁺ enhanced the red PL intensity in the Lu_2.94Al₅O₁₂:0.06Ce³⁺ phosphor.     

One-step synthesis of Sc2W3O12:Eu3+ phosphors with tunable luminescence for WLED

Sc₂W₃O₁₂ is an important host matrix for rare-earth doped luminescence. However, the conventional method to prepare the material is solid-state reaction, which results into coarse and irregular morphologies. In this work, Eu³⁺ doped Sc₂W₃O₁₂ phosphors with high crystallinity and pure phase were successfully synthesized via one-step hydrothermal method. It was found that the crystalline phase changed from Sc₂W₃O₁₂ phase to Na₄Sc₂(WO₄)₅ phase when the molar ratio between Sc(NO₃)₃ and Na₂WO₄ decreased. The temperature-dependent X-ray diffraction analysis was performed to prove the negative thermal expansion property of Sc₂W₃O₁₂. A systematic study on the effect of reaction time, temperature and Eu³⁺ doping concentration was explored. It was also found that the as-prepared samples displayed tunable emission colors, ranging from blueish white to orange red. Particularly, the white light emission with the chromaticity coordinate of (0.3395, 0.3289) can be realized in Sc₂W₃O₁₂: 5% Eu³⁺. What's more, the photoluminescence properties of the samples were investigated under different ambient temperatures between 97 and 280?K. The result clearly showed energy transfer between Eu³⁺ and WO₄^2?. The above results suggested that Sc₂W₃O₁₂:Eu³⁺ can be excellent candidate for solid-state lasing, panel display and WLEDs.     

Influence of multi-step annealing on nanostructure and surface morphology of Y2O3:SiO2 powder

Y₂O₃:SiO₂ powder was synthesized by a sol–gel method, using hydrous yttrium nitrate and hydrous silicon oxide as precursors and HCl as a catalyst. The dried samples were submitted to multi-step annealing schedule in air without applying pressure. A simple four-step annealing schedule with a final stage of about 900 °C for 6.0 h was followed. The samples of Y₂O₃:SiO₂ nanocomposites were obtained with well defined size and shape. Structural changes of the nanocomposites were investigated by XRD, FTIR and TEM. Multi-step annealing scheme with different ramp rates and incubation times allows recovery-relaxation processes within the boundaries and leading to a concomitant linear increase of crystallite size and densification. Almost fully dense quasi-spherical cubic-yttria nanopowder has been demonstrated with an average grain size distribution of 10–40 nm; can be uniformly dispersed in silica matrix.     

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.     

Thermal enhancement of up-conversion luminescence in Lu2W2.5Mo0.5O12: Er3+, Yb3+ phosphors

Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ phosphors were synthesized through high temperature solid state method. Under 980 nm laser excitation, the Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ compounds show thermal enhancement of up-conversion luminescence (UCL), which is attributed to the lattice contraction and distortion from negative thermal expansion (NTE) of Lu₂W_2.5Mo_0.5O₁₂ host enhancing the energy transfer of Yb³⁺ to Er³⁺, eliminating the energy transfer of Er³⁺ to Er³⁺ through Er³⁺ single-doped Lu₂W_2.5Mo_0.5O₁₂ phosphors without thermal enhancement of UCL. The green luminescence intensities at 693 K of the Lu_1.98-xW_2.5Mo_0.5O₁₂: 0.02Er³⁺, xYb³⁺ (x = 0.2, 0.3, 0.4) samples are 4.6, 4.3 and 7.0 times as that of 302 K, respectively. And through fluorescence intensity ratio (FIR) technique, the corresponding maximum absolute sensitivities are 0.00741, 0.00744 and 0.00723, respectively. The green monochromaticity of UCL spectra in Er³⁺/Yb³⁺ co-doped samples increase with the increasing of temperature, and the possible UCL mechanism with temperature was discussed. The results indicate that the Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ phosphors can be applied at a high temperature as optical thermometer with a good green monochromaticity.     

Synthesis and photoluminescence properties of CaGd2(MoO4)4:Eu3+ red phosphors

The novel red-emitting Eu³⁺ ions activated CaGd₂(MoO₄)₄ phosphors were prepared by a citrate sol–gel method. The X-ray diffraction patterns confirmed their tetragonal structure when the samples were annealed above 600 °C. The photoluminescence excitation spectra of CaGd₂(MoO₄)₄:Eu³⁺ phosphors exhibited the charge transfer band (CTB) and intense f–f transitions of Eu³⁺ ion. The optimized annealing temperature and Eu³⁺ ion concentration were analyzed for CaGd₂(MoO₄)₄:Eu³⁺ phosphors based on the dominant red (⁵D₀→⁷F₂) emission intensity under NUV (394 nm) excitation. All decay curves were well fitted by the single exponential function. These luminescent powders are expected to find potential applications such as WLEDs and optical display systems.     

Structural and optical investigations of Eu3+-doped TiO2 nanopowders

This paper presents an evaluation of photoluminescent and structural properties of Eu³⁺-doped TiO₂ materials in powder form prepared by sol–gel process. The increase of heat-treatment temperature of synthesis results in the TiO₂ phase transition, obtaining anatase, rutile and sometimes brookite, examined by Raman and XRD techniques. Crystallite size as well as microstrains in the crystal structure were evaluated as a function of Eu³⁺ and heat-treatment temperature. It was found that when Eu³⁺ is introduced in anatase phase an intense color emission is observed under excitation at 394 and 463 nm. The rutile phase presents inversion center symmetry, and apparently the Eu³⁺ tends to occupy this site, which decreases the intensity of the emission assigned to the ⁵D₀→⁷F₂ transition. The materials obtained at 700 °C showed most intensity of emission in the red region, verified by the ratio between ⁵D₀→⁷F₂/⁵D₀→⁷F₁ transitions of Eu³⁺. The results showed that the materials are interesting absorber in the ultraviolet and red region and can be used for improvement of energy conversion in solar cells devices.     

Photoluminescence and electron-beam excitation induced cathodoluminescence properties of novel green-emitting Ba4La6O(SiO4)6:Tb3+phosphors

Tb³⁺ions activated Ba₄La₆O(SiO₄)₆ (BLSO:Tb³⁺) phosphors were synthesized by a citrate sol-gel method. The X-ray diffraction pattern confirmed their oxyapatite structure. The field-emission scanning electron microscope image established that the BLSO:Tb³⁺phosphor particles were closely-packed and acquired irregular shapes. The photoluminescence (PL) excitation spectra of BLSO:Tb³⁺phosphors showed intense f–d transitions along with low intense peaks corresponding to the f–f transitions of Tb³⁺ions in the lower energy region. The PL emission spectra displayed the characteristic emission bands of Tb³⁺ions, and the optimized concentrations were found to be at 1 and 6 mol% for blue and green emission peaks, respectively. The cathodoluminescece (CL) spectra exhibited a similar behavior that was observed in the PL spectra except the intensity variations in the blue and green regions. The CL spectra of the BLSO:6 mol% Tb³⁺phosphor unveiled accelerating voltage induced luminescent properties.     

Effect of using different precursors on electrospinning of CaCu3Ti4O12

In this study, the rheological behavior of electrospinning solutions containing different copper and calcium salts (Cu(NO₃)₂·3H₂O, CuCl₂, Ca(NO₃)₂·4H₂O and CaCl₂) were investigated. To find out the suitable electrospinning solution for producing the high purity CaCu₃Ti₄O₁₂ nanofibers, solutions containing different copper and calcium salts were prepared and CaCu₃Ti₄O₁₂ fibers with different morphological and size were produced. The results showed that the nature of the metals complexes in the ceramic solutions had an obvious effect on the rheological behavior of the electrospinning solutions. FTIR spectras of the electrospinning solutions demonstrated that the interaction between the metal ions and carbonyl groups in the polyvinylpyrrolidone unit occurred and the polyvinylpyrrolidone chains underwent conformational variations. Intensity of the interaction between the metal ions and polymer chains in chloride salts solutions is more than nitrate salts solutions in order to the viscosities of chloride solutions that are more than nitrate solutions. So, thinner high purity polycrystalline CaCu₃Ti₄O₁₂ nanofibers with diameters ranging <200 nm were successfully synthesized by selecting a novel solution containing copper and calcium nitrates after sintering at 900 °C for 4 h.     

Near-infrared photo-responsive Er3+-K+ co-doped Y2O3 phosphors with enhanced UC luminescence

Y₂O₃: x% Er³⁺ (x=5, 7, 10, 12, 15) and Y₂O₃: 10% Er³⁺,x% K⁺ (x=0, 1, 3, 5, 7, 10, 15) phosphors were successfully prepared by a low-temperature combustion method. The structure as well as the absorption/emission spectra of phosphors were investigated. The effect of doping concentration of K⁺ ions on the upconversion (UC) luminescence of Y₂O₃: 10% Er³⁺ phosphor was examined and the possible optical transitions were discussed. The results showed that K⁺ ion doping not only changed the microstructure and crystallinity of the phosphors, but also enhanced its UC luminescence intensity. The Y₂O₃: 10% Er³⁺, 7% K⁺ phosphor exhibit the strongest UC emission intensity. Compared with the Y₂O₃: 10% Er³⁺ phosphor, the UC luminescence intensity at 563 nm and 661 nm was enhanced by 67.8 and 27.3 times for the K-codoped samples, respectively. The phosphor with the optimal doping concentration was mixed with a polymer to form a composite film, which was employed for the fabrication of near-infrared (NIR) photo-responsive detection devices. The device exhibited strong photo-current response to NIR light at 980 nm, implying that our work could inspire new design strategy for the development of NIR photo-detection devices.     

Enhanced luminescence of a Eu3+-activated double perovskite (Na,Li)LaMgWO6 phosphor based on A site inducing energy transfer

Li⁺ ion substituted Na_1−xLi_xLa_0.95Eu_0.05MgWO₆ phosphors were successfully synthesized by an improved sol-gel method using citric acid and polyethylene glycol as complexing agents. The structural evolution was systematically investigated by X-ray diffraction with Rietveld structure refinement and Raman spectra. The layered ordering of A-site cations and a second-order Jahn-Teller distortion of B’ cations simultaneously existed in this double perovskite. The decreased symmetry and lattice parameters within the same space group C2/m were observed from the Li⁺ substituted powders. Upon increasing the Li⁺ concentration, the absorption intensities of the 4f−4f transitions of Eu³⁺ monotonically increased. Likewise, the intensity of ⁵D₀-⁷F₂ monotonically increased under the excitations of both near-ultraviolet and blue light, with an enhancement of ten- and six-fold, respectively. The relative intensity ratio of red/orange emissions gradually increased, and the CIE chromaticity coordinates gradually approached those of standard red light. “A site inducing energy transfer” in double perovskite was achieved by selecting a substitution element with a small radius.     

Luminescence and self-referenced optical temperature sensing performance in Ca2YZr2Al3O12:Bi3+,Eu3+ phosphors

Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ phosphors were elaborated by a traditional solid-state reaction method. The luminescence of Ca₂YZr₂Al₃O₁₂:Bi³⁺ samples, energy transfer from Bi³⁺ to Eu³⁺, and the temperature sensing properties of Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ samples have been systematically researched. Under the excitation of ultraviolet light, Bi³⁺ single doped phosphors give 313 and 392 nm emission bands, which origin from the substitutions of Bi³⁺ instead of Ca²⁺ and Y³⁺ sites, respectively. And the color-adjustable emission from blue to red were observed by increasing Eu³⁺ content in Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ samples. Relying on different temperature dependent variation tendency, the fluorescence intensity ratio (FIR) values present outstanding temperature sensing properties. The absolute and relative sensitivity can be up to 0.826 %K^-1 and 0.664 %K^-1, respectively. All above results suggest that Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ phosphor is a potential alternative for optical thermometer.     

Site engineering of Ce3+-doped calcium scandate phosphors and understanding of relevant red-shifted emitting from green to yellow

CaSc₂O₄:Ce³⁺ is a well-known green emitting phosphor, but needs to match with suitable red emitting phosphors in practical white lighting. Herein, a site engineering strategy is proposed to modify the local coordination environment of Ce³⁺ by introducing Y³⁺ and Mg²⁺ ions into the CaSc₂O₄ crystal lattice. The obtained results indicate in the modified Ce³⁺-doped samples (CSO-YMg), Y³⁺ ions can occupy both Sc³⁺ and Ca²⁺ sites simultaneously, and the Y³⁺ ions tend to occupy Ca²⁺ sites in low-doped stage and enter into the Sc³⁺ sites in the high-doped stage. The introduction of Y³⁺ ions gives rise to the existence of MgO in as-prepared CSO-YMg samples, and it can be effectively washed through pickling. In the spectral aspect, with the increase of Y³⁺ and Mg²⁺ ions, the main emission peak is red-shifted from 512 nm to 530 nm upon excitation at 450 nm. However, the high-doped sample presents much stronger thermally induced fluorescence quenching than CaSc₂O₄:Ce³⁺. The lattice defects caused by doped ions (Y³⁺ and Mg²⁺) and the non-radiative energy transfer process between the Ca²⁺ (Ce³⁺) and Sc³⁺ (Ce³⁺ or Ce⁴⁺) sites should be responsible for such evident quenching phenomenon in CSO-YMg, which is obviously different from the emitting feature of CaSc₂O₄:Ce³⁺ (only at Ca²⁺ sites). Besides, utilizing the as-prepared CSO-5 phosphors and a blue LED (~450 nm), a WLED was successfully fabricated, yielding a comparable performance to those with commercial Y₃Al₅O₁₂:Ce³⁺ phosphors. What discussed in this study would bring some inspirations in the exploration and understanding of Ce³⁺-based phosphors according to local structural modification.     

Synthesis,structure and luminescence properties of a novel red fluorescent material Ba2MgB2O6:Eu3+

The crystal structure of Ba_2-xMgB₂O₆:xEu³⁺ phosphors, synthesized using a solid-state reaction, have been confirmed by X-ray diffraction analysis. This study focuses on the site occupancy preference of Eu³⁺ ions within the matrix, which was determined using bond energy theory, fluorescent spectra, and a consideration of energy transport and decay curves. The impact of Eu³⁺ ion concentration on luminescence has been assessed, and an optimal concentration (x = 0.22) identified. The critical distance, R_c was 9.6 Å, with a calculated θ value of 19.67, indicating that quadrupole-quadrupole interaction plays a critical role in the quenching Ba_2-xMgB₂O₆:xEu³⁺ phosphors. The Ba_2-xMgB₂O₆:xEu³⁺ phosphors exhibited a color purity of 99.26%, and a quantum efficiency of 49.68%. The activation energy Ea was determined to equal 0.2987 eV. The results have established Ba_1.78MgB₂O₆:0.22Eu³⁺ as a red fluorescent powder with high quantum efficiency and a millisecond fluorescence lifetime.     

Tunable luminescence and energy transfer properties of MgY4Si3O13: Ce3+, Tb3+, Eu3+ phosphors

The tricolor-emitting MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺ phosphors for ultraviolet-LED have been prepared via a high-temperature solid-state method. X-ray diffraction, photoluminescence emission, excitation spectra and fluorescence lifetime were utilized to characterize the structure and the properties of synthesized samples. Two different lattice sites for Ce³⁺ are occupied from the host structure and the normalized PL and PLE spectra. The emissions of single-doped Ce³⁺/Tb³⁺/Eu³⁺ are located in blue, green and red region, respectively. The energy transfer from Ce³⁺ to Tb³⁺ and from Tb³⁺ to Eu³⁺ has been validated by spectra and decay curves and the energy transfer mode from Tb³⁺ to Eu³⁺ was calculated to be electric dipole-dipole interactions. By adjusting the content of Tb³⁺ and Eu³⁺ in MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺, the CIE coordinates can be changed from blue to green and eventually generate white light under UV excitation. All the results indicate that the MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺ phosphors are potential candidates in the application of UV-WLEDs.