A reddish orange stoichiometric phosphor LiEu(PO3)4 for white light-emitting diodes

Stoichiometric phosphors LiGd_1−xEu_x(PO₃)₄(x=0, 0.2, 0.4, 0.6, 0.8, 1.0) were synthesized via traditional solid state reactions. The X-ray powder diffraction measurements show that all prepared samples are isostructural with LiNd(PO₃)₄. Eu³⁺ doped phosphors can emit intense reddish orange light under the excitation of near ultraviolet light from 370 to 410 nm. The strongest two at 591 and 613 nm can be attributed to the transitions from excited state ⁵D₀ to ground states ⁷F₁ and ⁷F₂, respectively. The typical chromaticity coordinates (x=0.620, y=0.368) of Eu³⁺ doped phosphors are in red area. The recorded absorbance spectra indicate that there is effective absorbance in the near UV region for all Eu³⁺ doped samples. Present research indicates that LiGd_1–xEu_x(PO₃)₄ is a promising phosphor for white light-emitting diodes.     

Tunable luminescence properties and efficient energy transfer in Eu,Mn co-doped Ba2MgP4O13

A series of Ba₂Mg_1−xMn_xP₄O₁₃ (x = 0-1.0) and Ba_1.94Eu_0.06Mg_1−xMn_xP₄O₁₃ (x = 0-0.15) phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), the photoluminescence spectra, and the decay curves are investigated. XRD analysis shows that the maximum tolerable substitution of Mn²⁺ for Mg is about 50 mol% in Ba₂MgP₄O₁₃. Mn²⁺-singly doped Ba₂MgP₄O₁₃ shows weak red-luminescence peaked at about 615 nm. The Eu²⁺/Mn²⁺ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 430 nm originating from Eu²⁺ and a broad red-emitting one peaked at 615 nm from Mn²⁺ ions. The luminescence of Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ in Ba₂MgP₄O₁₃. The efficient energy transfer from Eu²⁺ to Mn²⁺ is verified by the excitation and emission spectra together with the luminescence decay curves. The emission colors could be tuned from the blue to the red-purple and eventually to the deep red. The resonance-type energy transfer via a dipole-quadrupole interaction mechanism is supported by the decay lifetime data. The energy transfer efficiency and the critical distance are calculated and discussed. The temperature dependent luminescence spectra of the Eu²⁺/Mn²⁺ co-doped phosphor show a good thermal stability on quenching effect.     

Enhanced luminescence of novel Ca3B2O6:Dy phosphors by Li-codoping for LED applications

The Ca_3−xB₂O₆:xDy³⁺ (0.0 ≤ x ≤ 0.105) and Ca_2.95−yDy_0.05B₂O₆:yLi⁺ (0 ≤ y ≤ 0.34) phosphors were synthesized at 1100 °C in air by solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), photoluminescence excitation (PLE) and photoluminescence (PL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm is due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions upon 350 nm excitation is observed at 480 nm (blue) due to the ⁴F_9/2 → ⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2 → ⁶H_13/2 transitions and a weak 660 nm (red) due to ⁴F_9/2 → ⁶H_11/2 emissions, respectively. The optimal PL intensity of the Ca_3−xB₂O₆:xDy³⁺ phosphors is found to be x = 0.05. Moreover, the PL results from Ca_2.95−yDy_0.05B₂O₆:yLi⁺ phosphors show that Dy³⁺ emissions can be enhanced with the increasing codopant Li⁺ content till y = 0.22. By simulation of white light, the CIE of the investigated phosphors can be tuned by varying the content of Li⁺ ions, and the optimal CIE value (0.300, 0.298) is realized when the content of Li⁺ ions is y = 0.22. All the results imply that the Ca_2.95−yDy_0.05B₂O₆:yLi⁺ phosphors could be potentially used as white LEDs.     

Synthesis and photoluminescence properties of MgAl(PO4)O:Eu red phosphor for white LEDs

Eu³⁺-activated MgAl(PO₄)O:phosphor has been synthesized by a high temperature solid state reaction and efficient red emission under near-ultraviolet excitation is observed. The emission spectrum shows a dominant peak at 594 nm due to the ⁵D₀→⁷F₁ transition of Eu³⁺. The excitation spectrum is coupled well with the emission of UV LED (350–410 nm). The effect of Eu³⁺ concentration on the luminescent properties of MgAl(PO₄)O:Eu³⁺ and the mechanism of concentration quenching of Eu³⁺ are studied. The results show that MgAl(PO₄)O:Eu³⁺ is a promising red-emitting phosphor for white LEDs.     

Enhanced photoluminescence property of Dy co-doped BaAl2O4:Eu green phosphors

Eu²⁺-doped BaAl₂O₄ green phosphors were prepared by a conventional solid-state reaction and the effects of Dy³⁺ co-doping on the photoluminescence property were investigated. The phosphors were characterized by X-ray powder diffraction (XRD), fluorescence spectroscopy, field-emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS). XRD showed that all prepared samples exhibited a hexagonal BaAl₂O₄ phase. Fluorescence spectroscopy showed that the photoluminescence efficiency increased with increasing Eu²⁺ concentration until 3 mol% then decreased at higher concentrations due to concentration quenching effect. Moreover, Dy³⁺ co-doping increased the photoluminescence efficiency of the Eu²⁺-doped BaAl₂O₄ phosphor.     

Synthesis and emission analysis of RE (Eu or Dy):Li2TiO3 ceramics

The development and photoluminescence analysis of Eu³⁺or Dy³⁺ ions in the matrix of lithium titanate (Li₂TiO₃) ceramics by using a solid state reaction method are reported. Emission spectra of Eu³⁺:Li₂TiO₃ ceramics have shown strong red emission at 611 nm (⁵D₀ → ⁷F₂) with λ_exci = 392 nm (⁷F₀ → ⁵L₆) and from the Dy³⁺:Li₂TiO₃, a blue emission at 493 nm (⁴F_9/2 → ⁶H_15/2) and also an yellow emission at 582 nm (⁴F_9/2 → ⁶H_13/2) have been observed with λ_exci = 366 nm (⁶H_15/2 → ⁶P_5/2). Both the rare-earth ions containing ceramics have displayed their brighter emission performance from their measured spectral results. In addition, X-ray diffraction (XRD), Fourier transform infra red (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) have been used to characterize the structural properties of (Eu³⁺ or Dy³⁺):Li₂TiO₃ ceramics.     

Synthesis and luminescent characteristics of yellow emitting GdSr2AlO5:Ce phosphor for blue light based white LED

A series of Ce³⁺ ions doped GdSr₂AlO₅ (GSA) phosphors were synthesized by a citric acid based sol–gel method. The X-ray diffraction patterns confirmed their tetragonal structure after the samples were annealed at 1300 °C, and the scanning electron microscope image showed the closely packed particles. The excitation spectra revealed that the GSA phosphor effectively excited with blue light of 442 nm due to the 4f¹→5d¹ transition and exhibited yellow emission corresponding to the 5d¹→4f¹ transition of Ce³⁺ ions. The optimum doping concentration of Ce³⁺ ions was 5 mol% and the critical distance was calculated to be ~17 Å. White LEDs were fabricated by combining blue LED (465 nm) chip with Ce³⁺:GSA phosphor. The CIE chromaticity coordinates (0.34, 0.31) provide their emission potentiality in the white light region.     

Luminescent properties of a novel afterglow phosphor Sr3Al2O5Cl2:Eu,Ce

A series of Eu²⁺ and Ce³⁺ doped/co-doped Sr₃Al₂O₅Cl₂ afterglow phosphors that presented various bright colors were successfully synthesized via high temperature solid state reaction. The structure and luminescence properties of the obtained samples were characterized by X-ray powder diffraction (XRD), photoluminescence (PL) spectra and decay curves as well as the thermoluminescence (TL) glow curves. The XRD results showed that all the phase could be indexed to the orthorhombic structure with the space group P2₁2₁2₁. After being exposed to a 254 nm or 365 nm mercury lamp, blue/yellow-orange afterglow emissions with broad bands peaking around 620 nm/435 nm, which were ascribed to the characteristic 4f⁶5d–4f⁷/5d¹–4f¹ transitions of Eu²⁺/Ce³⁺, could be observed in phosphors of Sr₃Al₂O₅Cl₂:Eu²⁺/Sr₃Al₂O₅Cl₂:Ce³⁺, respectively. Because of the overlap spectral range between the Sr₃Al₂O₅Cl₂:Eu²⁺ and Sr₃Al₂O₅Cl₂:Ce³⁺ phosphors, the energy transfer (ET) from Ce³⁺ to Eu²⁺ occurred. The related ET process was discussed in detail. Moreover, the incorporation of Ce³⁺ could significantly prolong the afterglow duration of Sr₃Al₂O₅Cl₂:Eu²⁺ phosphor, which was due to the increase of trap concentration. Consequently, 6 h of the afterglow duration could be observed in Sr₃Al₂O₅Cl₂:1.0%Eu²⁺, 0.5%Ce³⁺ sample, exhibiting much longer than that of Sr₃Al₂O₅Cl₂: 1.0%Eu²⁺ (3 h). From the afterglow decay curves and the fitting results, the optimal concentration of Ce³⁺ for the enhanced afterglow property was experimentally determined to be 0.5%.     

Preparation of Ca4Mg5(PO4)6:Eu,Mn phosphor and its photoluminescence properties

Eu²⁺ and Mn²⁺ singly doped and Eu²⁺/Mn²⁺-codoped Ca₄Mg₅(PO₄)₆ phosphors were synthesized via combustion synthesis. Mn²⁺-singly doped Ca₄Mg₅(PO₄)₆ phosphor exhibits a single red emission in the wavelength range of 500–700 nm due to the ⁴T₁(⁴G)→⁶A₁(⁶S) transition of Mn²⁺. Eu²⁺/Mn²⁺ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 442 nm originating from Eu²⁺ and a broad red-emitting one peaked at 609 nm from Mn²⁺. Energy transfers from Eu²⁺ to Mn²⁺ were discovered by directly observing significant overlap of the excitation spectrum of Mn²⁺ and the emission spectrum of Eu²⁺ as well as the systematic relative decline and growth of emission bands of Eu²⁺ and Mn²⁺, respectively. Based on the principle of energy transfer, the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺.     

Solvothermal synthesis of red and green emitting Ca1.65Sr0.35SiO4:Eu and Ca1.65Sr0.35SiO4:Eu phosphors for solid-state lighting applications

A novel and facile synthetic approach has been trialed, and attempted with success in the preparation of two phosphors namely, a red emitting CaSrSiO₄:Eu³⁺ and a green emitting CaSrSiO₄:Eu²⁺. These phosphors were successfully synthesized using a simple co-precipitating solvo-thermal strategy wherein tetraethyl orthosilicate (TEOS) as silica source and the acetate precursors of strontium (Sr²⁺), calcium (Ca²⁺) and europium (Eu³⁺) are utilized. The material so obtained is subjected to an extensive photoluminescence behavior study. The concentration of the dopant (Eu³⁺and Eu²⁺) plays a significant role in the determination of photoluminescence behavior and hence a systematic and in-depth experimental studies were done and the results are synchronized. On interpretation of the output, it came to light that an intense emission signals sparked in the red region (590 and 615 nm) in the case of phosphor doped with Eu³⁺, which is excited under near ultra violet (395 nm) and blue (466 nm) region. In case of the CaSrSiO₄ sample doped with Eu²⁺_, an intense broad green signal (~510 nm) is obtained under the excitation range of 350–430 nm. The results obtained are quite encouraging and made a strong confirmation as, the solvo-thermally synthesized CaSrSiO₄, which is activated by the dopants namely Eu³⁺ and Eu²⁺ possesses an immense potential and it is exactly tapped by the adopted methodology. Despite its strong impact, it will also assure a strong revolution in the fabrication and thus the commercialization of white LEDs as both the red and green emitting phosphor.     

Luminescent properties of Sr2B2O5: Tm,Na blue phosphor

A novel blue phosphor, Sr₂B₂O₅: Tm³⁺, Na⁺ for white light-emitting diodes (W-LEDs) was prepared by solid-state synthesis and its structure and luminescence properties were investigated. This phosphor can be effectively excited within the broad near ultraviolet (NUV) wavelength region, from 340 nm to 370 nm, and exhibits a satisfactory blue performance. The emission peaks are observed at 457 nm (blue) and 475 nm (blue), due to the respective transitions of ¹D₂→³F₄ and ¹G₄→H₆. Seven mole percent of doping concentration of Tm³⁺ was shown to be optimal. Concentration quenching occurs when Tm³⁺ concentration is beyond 7 mol%, its mechanism being explained by dipole–dipole interaction of Tm³⁺ and being confirmed by decay property measurements. We have made a deep analysis on the effect of charge compensation reagent on luminescence intensity. Good blue emissions with the CIE chromaticity coordinates (0.173, 0.165) could be achieved. Our results suggest that the Sr₂B₂O₅: Tm³⁺, Na⁺ phosphor is a potential blue-emitting material.     

Multifuctional Fe3O4@C/YVO4:Dy nanopowers: Preparation,luminescence and magnetic properties

As-synthesized Fe₃O₄ nanoparticles were encapsulated with carbon layers through a simple hydrothermal process. Fe₃O₄/C nanoparticles were coated with YVO₄:Dy³⁺ phosphors to form bifunctional Fe₃O₄@C@YVO₄:Dy³⁺ composites. Their structure, luminescence and magnetic properties were characterized by XRD, SEM, TEM, HRTEM, PL spectra and VSM. The experimental results indicated that the as-prepared bifunctional composites displayed well-defined core–shell structures. The ∼12 nm diameter YVO₄:Dy³⁺ shell exhibited tetragonal structure. Additionally, the composites exhibited a high saturation magnetization (13 emu/g) and excellent luminescence properties, indicating their promising potential as multifunctional biosensors for biomedical applications.     

Synthesis and optical characterization of novel Sr3Ga2O6:Eu phosphor

Alkaline earth metal gallets have been identified as an important ceramic material. The crystal chemistry of many of these gallets is well explored; however, very rare studies regarding optical properties of rare earth (RE) ions doped in such gallets, particularly in Sr₃Ga₂O₆ host, have been carried out. The present study reports on synthesis and characterization of novel Sr₃Ga₂O₆:Eu³⁺ phosphors. The phosphors have been synthesized using a conventional solid state reaction method. Crystal structure, morphology and luminescence properties (excitation, emission and CIE coordinate) of these phosphors have been studied as a function of sintering temperature and Eu³⁺ concentration. X-ray diffraction study reveals that the phosphor sintered at low temperature (900 °C) contains an impurity phase which is removed at higher sintering temperatures and results into cubic crystalline phase of Sr₃Ga₂O₆. Particle size of the phosphor increases with an increase in sintering temperature which results to a red shift in the peak position of excitation band lying in a broad range from 250 to 370 nm. Optimum emission intensity is attained for 0.12 mol% concentration of Eu³⁺ ions; above this concentration, a quenching in emission intensity is observed.     

Synthesis and photoluminescence properties of Eu doped Sr9Sc(PO4)7 phosphors for white light-emitting diodes

A series of Eu²⁺-activated Sr₉Sc(PO₄)₇ yellowish-green emitting phosphors were synthesized by conventional solid-state reaction. The photoluminescence (PL) properties and concentration quenching mechanism of the as-prepared phosphors were investigated. The emission spectrum exhibits a broad and asymmetric band peaking at 510 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺. The excitation spectrum exhibits a broad band extending from 250 to 450 nm, which matches well with the emission of near ultraviolet (n-UV) chips (350–430 nm). Non-radiative transitions between Eu²⁺ ions in the Sr₉Sc(PO₄)₇ host have been demonstrated to be attributable to dipole–dipole interactions, and the critical distance was calculated to be 23.1 Å. These results indicate that Sr₉Sc(PO₄)₇:Eu²⁺ phosphor could serve as a promising candidate for application in n-UV white-light LEDs.     

The effect of concentration of Dy ions on luminescence properties of Y2O2S:Dy,Mg, Ti phosphors

Y₂O₂S:Dy³⁺, Mg²⁺, Ti⁴⁺ white-light long-lasting phosphors were synthesized by the sol–gel method. The effect of Dy³⁺ doping concentration on the luminescence properties was investigated. The samples were characterized by X-ray diffraction, photoluminescence spectroscopy and thermally stimulated spectrometry. The samples doped with different concentrations of Dy³⁺ ions were composed of the pure Y₂O₂S phase. Under 359 nm UV excitation, the phosphor presented white luminescence due to mixing of the dominating emissions centered at 488 nm (blue) and 579 nm (yellow), corresponding to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions of Dy³⁺, respectively. When Dy³⁺ concentration was 1 mol%, the CIE chromaticity diagram was (0.375,0.374), and the decay time could last for over 65 min (≥1 mcd/m²).     

Mechanochemical synthesis of YNbO4:Eu nanocrystalline powder and its structural,microstructural and photoluminescence properties

In this research we prepared nanocrystalline YNbO₄:Eu³⁺ phosphor, i.e. nanophosphor, powder using an efficient mechanochemical method followed by annealing. X-ray diffraction analysis revealed that YNbO₄:Eu³⁺ crystallizes in monoclinic structure C2/c where, from the point of view of A and B in ABO₄ compounds, cation coordination can be noted as [6+2, 4+2]. Crystallite size of about 40 nm, was estimated using Debye Scherrer's equation. Raman spectroscopy with 785 and 532 nm excitation wavelengths is performed to record a majority of materials phonon modes and to provide more in depth understanding of the YNbO₄ structure. Scanning electron microscopy observations indicate that the mechanical treatment during synthesis is causing non-uniformity of the powder microstructure. High resolution photoluminescent measurements upon UV excitation showed intense emission coming from f–f transitions of the europium ion with the lifetime of 0.68 ms, suggesting that the obtained YNbO₄:Eu³⁺ is a good potential phosphor. A comparison of emissive properties with microcrystalline YNbO₄:Eu³⁺ was made and it showed higher values of emission intensity and lifetime of the nanocrystalline sample.     

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.     

Effect of sintering atmosphere and lithium ion co-doping on photoluminescence properties of NaCaPO4:Eu phosphor

This paper reports on the photoluminescence properties of Na_1−yLi_yCa_1−xPO₄:_xEu²⁺ phosphors synthesized by a solid state reaction method. The prepared phosphors have been thoroughly characterized by means of X-ray diffraction (XRD), Field-emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectrum (FTIR), Raman spectrum, Thermo gravimetric and differential thermal analysis (TG–DTA) and photoluminescent spectral measurements. The structure of Na_1−yLi_yCa_1−xPO_4:xEu²⁺ phosphors were found to be orthorhombic in nature with a sphere-like morphology and having the particle size in micrometer range. The excitation spectra of NaCaPO₄:Eu²⁺ phosphors revealed a broad excitation band having its maximum intensity at 373 nm and ranging from 250 m to 450 nm. Incidentally, it matches well with the ultraviolet (UV) radiation of light-emitting diodes (LEDs). Upon 373 nm excitation, these phosphors exhibited intense bluish-green emission band centered at 505 nm. The effect of sintering atmospheres and co-doping of lithium ions on the photoluminescence properties of the NaCaPO₄:Eu²⁺ phosphors were studied and explained suitably. The obtained results indicate that the prepared NaCaPO₄:Eu²⁺ phosphors are promising bluish-green candidates for the phosphor-converted white LED applications.     

White light emission from Eu co-activated Ca2Gd8Si6O26:Dy nanophosphors by solvothermalsynthesis

Ca₂Gd₈(SiO₄)₆O₂ (CGS) nanophosphors with different concentrations of single-doped Dy³⁺ ions and co-doped Dy³⁺/Eu³⁺ ions were prepared by a solvothermal synthesis. Very fine particles in the nanometer range could be achieved by this method, as evidenced by transmission electron microscope measurements. The hexagonal phase of the oxyapatite structure was confirmed by X-ray diffraction patterns. The energy transfer between Eu³⁺ and Dy³⁺ ions was investigated by photoluminescence excitation and emission properties. These phosphors had absorption bands in the UV and NUV region, which are suitable for the emission wavelength of UV or NUV light-emitting diodes (LEDs). With increasing the Eu³⁺ ion concentration, the emission peak intensity corresponding to the ⁵D₀→⁷F₂ transition increased and the yellow (⁴F_9/2→⁶H_13/2) emission intensity also increased compared to the blue (⁴F_9/2→⁶H_15/2) emission intensity due to the increased energy transfer between Dy³⁺ to Eu³⁺ ions. Thus, the Eu³⁺ ions compensated the red emission component of the Dy³⁺ doped CGS nanophosphors. Such phosphors are expected to have potential applications for NUV based white LEDs.     

Single-phased emission-tunable Ca3Si2O7:Ce,Eu phosphors for white light-emitting diodes

A series of single-phased emission-tunable Ca₃Si₂O₇:Ce³⁺, Eu²⁺ phosphors has been prepared by the solid-state reaction method. The phosphors show two intense emission bands at about 450 nm and 610 nm, which are attributed to the 5d→4f transitions of Ce³⁺ and Eu²⁺ ions, respectively. The emission colors of Ca₃Si₂O₇:Ce³⁺, Eu²⁺ phosphors vary from blue (0.148, 0.147) to white (0.309, 0.260), and eventually to orange (0.407, 0.319) by tuning the Eu²⁺/Ce³⁺ ratio. Energy transfer from Ce³⁺ to Eu²⁺ is studied by luminescence spectra and energy transfer efficiency. The results show an electric quadrupole–quadrupole interaction plays an important role in the process of energy transfer. The phosphors with tunable emission are suitable for application in white light-emitting diodes.