The structure and luminescence properties of Mn2+/Eu2+/Er3+‐doped MgO‐Ga2O3‐SiO2 glasses and glass‐ceramics

The MgO–Ga₂O₃–SiO₂ glasses and glass‐ceramics samples doped with Eu²⁺/Mn²⁺/Er³⁺ and heated in reductive atmosphere were prepared by the sol–gel method. The structure, morphology and the luminescence properties were studied using X‐ray diffraction, high‐resolution transmission electron microscope, fluorescence spectra, and up‐conversion emission. The luminescence characteristics of doped ions could be influenced by temperature and matrix component. The characteristic emission of Mn²⁺, Eu²⁺ and Er³⁺ were seen and the energy transfer efficiency from Eu²⁺ to Mn²⁺ was enhanced as Mn²⁺ concentration was increased. In addition, the two‐photon process was determined for the Er³⁺‐doped samples.     

Photoluminescence,cathodoluminescence and thermal stability of Sm3+‐activated Sr3La(VO4)3 red‐emitting phosphors

A series of Sm³⁺‐activated Sr₃La(VO₄)₃ phosphors were synthesized by a facile sol‐gel method. X‐ray diffraction patterns and photoluminescence (PL)/cathodoluminescence (CL) spectra as well as PL decay curves were employed to characterize the obtained samples. Upon 402 nm light excitation, the characteristic emissions of Sm³⁺ ions corresponding to ⁴G_5/2→⁶H_J transitions were observed in all the as‐prepared products. The PL emission intensity was increased with increase in Sm³⁺ ion concentration, while concentration quenching occurred when the doping concentration was over 4 mol%. The non‐radiative energy transfer mechanism for concentration quenching of Sm³⁺ ions was dominated by dipole–dipole interaction and the critical distance was around 21.59 Å. Furthermore, temperature‐dependent PL emission spectra revealed that the obtained phosphors possessed good thermal stability with an activation energy of 0.19 eV. In addition, the CL spectra of the samples were almost the same as the PL spectra, and the CL emission intensity showed a tendency to increase with increase in accelerating voltage and filament current. These results suggest that the Sm³⁺‐activated Sr₃La(VO₄)₃ phosphors with good color coordinates, high color purity and superior thermal stability may be a potential candidate for applications in white light‐emitting diodes and field‐emission displays as red‐emitting phosphors.     

Sol–gel synthesis,characterization and luminescence properties of SrMgAl2SiO7:Eu2+ as a novel nanocrystalline phosphor

In this research, a new SrMgAl₂SiO₇:Eu²⁺ phosphor was synthesized via the sol–gel method. The phase‐forming processes were studied by thermogravimetric–differential thermal analysis and X‐ray diffraction technique. Scanning electron microscopy showed that there is uniform morphology and microstructure owing to the sol–gel route. Spectrophotometry and colorimetry analyses illustrated that, under short ultraviolet excitation, the main emission peak occurred at 421 nm and also a relatively pure blue color was observed that was ascribed to the 4f⁶5d¹(²D) → 4f⁷(⁸S_7/2) transition of Eu²⁺ with color coordination of x = 0.187, y = 0.077. Finally, it was found that the color and phase purity of the synthesized powder increased as calcinations time increased. Copyright © 2010 John Wiley & Sons, Ltd.     

Enhanced photoluminescence of the Ca0.8Zn0.2TiO3:0.05% Pr3+ phosphor by optimized hydrothermal conditions

The red‐emitting phosphor Ca_0.8Zn_0.2TiO₃:Pr³⁺ was synthesized using an ethylene glycol (EG)‐assisted hydrothermal method. The effects of additional amounts of and order of adding EG, plus hydrothermal temperature, time, and pH on the composition, morphology and optical properties of the titanate phosphors were studied. The crystalline phases of the titanate phosphors were confirmed to be constituted of a series of co‐existing CaTiO₃, Zn₂TiO₄ and Ca₂Zn₄Ti₁₆O₃₈ compounds in various proportions that were visualized using an X‐ray diffractometer (XRD). The optical properties of the phosphors were studied using photoluminescence spectra and UV–visible spectroscopy. The results show that the impurities Zn₂TiO₄:Pr³⁺ and Ca₂Zn₄Ti₁₆O₃₈:Pr³⁺ significantly contributed to the enhancement of an absorption band around 380 nm. The optimum Ca_0.8Zn_0.2TiO₃:Pr³⁺ phosphor consisting of appropriate amounts of CaTiO₃, Ca₂Zn₄Ti₁₆O₃₈ and Zn₂TiO₄ in three phases was achieved by controlling the hydrothermal conditions, and the obtained red phosphor exhibited the highest red emission (¹D₂ → ³H₄ transition of Pr³⁺) with an ideal chromaticity coordinate located at (x = 0.667, y = 0.332) under 380 nm excitation.     

Luminescence properties of novel deep‐red‐emitting Ca3Al2Ge2O10:Cr3+ phosphors

Ca₃Al₂Ge₂O₁₀:Cr³⁺ phosphors were prepared by a high‐temperature solid‐state method, and their luminescence properties were investigated. Under excitation at 550 nm, Ca₃Al₂Ge₂O₁₀:Cr³⁺ phosphors exhibited a broad red emission band at 697 nm in the range 650–750 nm that was caused by the ²E→⁴A₂ transition of Cr³⁺. For the 697 nm emission peak, emission intensity reached a maximum at x = 0.07, and there was concentration quenching of Cr³⁺ in Ca₃Al₂Ge₂O₁₀; the corresponding concentration quenching mechanism was analysed. Under excitation at 262 nm, the Ca₃Al₂Ge₂O₁₀:Cr³⁺ phosphor showed a weakly broad emission band in the range 350–600 nm that was caused by intrinsic defects (V′′_Ca and V′′_O). Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and luminescence properties of blue‐emitting phosphor Ca12Al14O32F2:Eu2+ for white light‐emitting diode

A blue‐emitting phosphor Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ was synthesized using a high‐temperature solid‐state reaction under a reductive atmosphere. The X‐ray diffraction measurements indicate that a pure phase Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ can be obtained for low doping concentration of Eu²⁺. The phosphor has a strong absorption in the range 270–420 nm with a maximum at ~340 nm and blue emission in the range 400–500 nm with chromatic coordination of (0.152, 0.045). The optimal doping concentration is ~0.24. In addition, the luminescence properties of the as‐synthesized phosphor were evaluated by comparison with those of Ca₁₂Al₁₄O₃₂Cl₂:Eu²⁺ and the commercially available phosphor BaMgAl₁₀O₁₇:Eu²⁺. The emission intensity of Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ was ~72% that of BaMgAl₁₀O₁₇:Eu²⁺ under excitation at λ = 375 nm. The results indicate that Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ has potential application as a near‐UV‐convertible blue phosphor for white light‐emitting diodes.     

Study of luminescence and effect of Dy3+ on NaMgSO4Cl:Ce chlorosulphate phosphor

Chlorosulphate NaMgSO₄Cl phosphor doped with Ce³⁺ and co‐doped by Dy³⁺ prepared by the wet chemical method was studied for its photoluminescence and thermoluminescence (TL) characteristics. The emission spectrum of Ce³⁺ shows dominant peaks at 346 nm (excitation 270 nm) due to 5d → 4f transition. Efficient energy transfer occurs from Ce³⁺ → Dy³⁺ ions. Dy³⁺ emission at 485 nm and 576 nm is due to ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ion respectively. The TL glow curves of NaMgSO₄Cl:Ce and Ce,Dy have been recorded for various concentrations at a heating rate of 2 °C/s irradiated by γ‐rays at a dose rate of 0.995 kGy/h for 1 Gy, which peaks at about 241 °C and 247‐312 °C respectively. Further, in changing the concentration level, the general structure of the intensity is found to increase. The main property of this phosphor is its sensitivity even for low concentrations of rare earth ions and low γ‐ray dose. There is still scope for higher doses of γ‐radiation. The phosphor presented may be used as a lamp phosphor as well as for TL studies. Copyright © 2014 John Wiley & Sons, Ltd.     

Probing the optical properties and luminescence mechanism of a UV‐emitting SrBPO5:Ce3+ phosphor

Ce‐doped (1 × 10^?5 to 3.0 mol%) SrBPO₅ phosphors were synthesized using a conventional solid‐state reaction route at 1273 K in an air atmosphere. Phase and morphology of the samples were studied from powder X‐ray diffraction (XRD) patterns and scanning electron microscope (SEM) micrographs, respectively. The band gap energies of the pure and Ce‐doped SrBPO₅ phosphors were calculated from the recorded diffuse reflectance spectra. Photoluminescence (PL) and Ce³⁺ lifetime were recorded at 300 and 77 K. Photoluminescence lifetime measurements revealed two‐lifetime values for Ce³⁺ at both 300 K (17 and 36 nsec) and 77 K (12 and 30 nsec), suggesting the presence of two different environments around Ce³⁺. Time‐resolved emission spectroscopy (TRES) studies confirmed the presence of Ce³⁺ in two different environments. In addition, SrBPO₅:Ce exhibited intense UV emission, signifying its possible use as an efficient sensitizer for solid‐state lighting applications. The effect of γ‐irradiation on PL was also determined. Thermally stimulated luminescence (TSL) glow curves of the γ‐irradiated phosphor, along with trap parameters, dose–response, and the possible TSL mechanism were also investigated. Positron annihilation lifetime spectroscopy was carried out to probe defects present in undoped and Ce‐doped SrBPO₅.     

Investigation of UV‐emitting Gd3+‐doped LiCaBO3 phosphor

Incorporating the Gd³⁺ rare earth ion in the LiCaBO₃ host lattice resulted in narrow‐band UV‐B emission peaking at 315 nm, with excitation at 274 nm. The LiCaBO₃:Gd³⁺ phosphor was synthesized via the solid‐state diffusion method. The structural, morphological and luminescence properties of this phosphor were characterized by X‐ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and photoluminescence (PL) spectroscopy. Electron paramagnetic resonance (EPR) characterization of the as‐prepared phosphors is also reported here. XRD studies confirmed the crystal formation and phase purity of the prepared phosphors. A series of different dopant concentrations was synthesized and the concentration‐quenching effect was studied. Critical energy transfer distance between activator ions was determined and the mechanism governing the concentration quenching is also reported in this paper. Copyright © 2015 John Wiley & Sons, Ltd.     

Sol‐gel synthesis and luminescent properties of red‐emitting Y(P,V)O4:Eu3+ phosphors

Eu³⁺‐activated Y(P,V)O₄ phosphors were prepared by the EDTA sol‐gel method, and the corresponding morphologies and luminescent properties were investigated. The sample particles were relatively spheroid with size of 2–3 µm and had a smooth surface. The excitation spectra for Y(P,V)O₄:Eu³⁺ consisted of three strong excitation bands in the 200–350 nm range, which were attributed to a Eu³⁺‐ O^2? charge‐transfer band and ¹A₁?¹ T₁/¹ T₂ transitions in VO₄^3?. The as‐synthesized phosphors exhibited a highly efficient red luminescence at 613 nm due to the Eu^{3+ 5}D₀?⁷ F₂ electric dipole transition. With the increase in the V⁵⁺/P⁵⁺ ratio, the luminescence intensity of the red phosphor under UV excitation was greatly improved due to enhanced VO₄^3? → Eu³⁺ energy transfer. Copyright © 2015 John Wiley & Sons, Ltd.     

Crystal structure and luminescence properties of the blue‐green‐emitting Ba9(Lu,Y)2Si6O24:Ce3+ phosphor

Samples of the Ba₉(Lu_2‐xY_x)Si₆O₂₄:Ce³⁺ (x = 0–2) blue‐green phosphors were synthesized by solid‐state reactions. All the samples exhibited a rhombohedral crystal structure. As the Y³⁺ concentration increased, the diffraction peaks shifted to the small angle region and the lattice parameters increased due to the larger ionic radius of Y³⁺ (r = 0.900 Å) compared with that of Lu³⁺ (r = 0.861 Å). Under 400 nm excitation, samples exhibited strong blue‐green emissions around 490 nm. The emission bands had a slight blue shift that resulted from weak crystal‐field splitting with increasing Y³⁺ concentration. Luminescence intensity and quantum efficiency (QE) decreased with increasing Y³⁺ concentration. The internal QE decreased from 74 to 50% and the external QE decreased from 50 to 34% as x increased from 0 to 2. The thermal stability of the Lu series was better than that of the Y‐series. The excitation band peak around 400 nm matched well with the emission light from the efficient near‐ultraviolet (NUV) chip. These results indicate promising applications for these NUV‐based white light‐emitting diodes.     

Luminescence properties of a novel red phosphor 6LaPO4–3La3PO7–2La7P3O18:Eu3+

Eu³⁺‐doped 6LaPO₄–3La₃PO₇–2La₇P₃O₁₈ red luminescent phosphors were synthesized by co‐deposition and high‐temperature solid‐state methods and its polyphase state was confirmed by X‐ray diffraction analysis. Transmission electron microscopy showed the grain morphology as a mixture of rods and spheres. Luminescence properties of the phosphor were investigated and its red emission parameters were evaluated as a function of Eu³⁺ concentration (3.00–6.00 mol%). Excitation spectra of 6LaPO₄–3La₃PO₇–2La₇P₃O₁₈:Eu³⁺ showed strong absorption bands at 280, 395, and 466 nm, while the luminescence spectra exhibited prominent red emission peak centred at 615 nm (⁵D₀→⁷F₂) in the red region. CIE chromaticity coordinates of the 6LaPO₄–3La₃PO₇–2La₇P₃O₁₈:5%Eu³⁺ phosphor were (0.668, 0.313) in the red region, and defined its potential application as a red phosphor.     

Synthesis and luminescence properties of Ca3Ga2Si3O12:RE3+ (RE = Eu/Tb) powder phosphors

Rare earth ions (Eu³⁺ or Tb³⁺)‐activated Ca₃ Ga₂ Si₃O₁₂ (CaGaSi) phosphors were synthesized by using a sol–gel method. Photoluminescence spectra of Eu³⁺:CaGaSi phosphors exhibited five emission bands at 578, 592, 612, 652 and 701 nm, which were assigned to the transitions (⁵D₀ → ⁷F₀, ⁷F_1, ⁷F₂, ⁷F₃ and ⁷F₄), respectively, with an excitation wavelength of λ_exci = 392 nm. Among these, the transition ⁵D₀ → ⁷F₂ (612 nm) displayed bright red emission. In the case of Tb³⁺:CaGaSi phosphors, four emission bands were observed at 488 (⁵D₄ → ⁷F₆), 543 (⁵D₄ → ⁷F₅), 584 (⁵D₄ → ⁷F₄) and 614 nm (⁵D₄ → ⁷F₃) from the measurement of PL spectra with λ_exci = 376 nm. Among these, the transition ⁵D₄ → ⁷F₅ at 543 nm displayed bright green emission. The structure and morphology of the phosphors were studied from the measurements of X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy‐dispersive X‐ray analysis (EDAX) results. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and luminescence characterization of Y2BaZnO5:RE (RE = Eu3+, Tb3+, Pr3+ and Sm3+) phosphors

Modified synthesis and luminescence of Y₂BaZnO₅ phosphors activated with the rare earths (RE) Eu³⁺, Tb³⁺, Pr³⁺ and Sm³⁺ are reported. RE₂BaZnO₅ phosphors have attracted attention because of their interesting magnetic and optical properties; and are usually prepared using a two‐step solid‐state reaction. In the first step, carbonates or similar precursors are thoroughly mixed and heated at 900°C to decompose them to oxides. To eliminate the unwanted phases like BaRE₂O₄, the resulting powders are reheated at 1100°C for a long time. We prepared Y₂BaZnO₅ phosphors activated with various activators by replacing the first step with combustion synthesis. The photoluminescence results are presented. The photoluminescence results for Eu³⁺, Tb³⁺ and Pr³⁺ are in good agreement with the literature. However, photoluminescence emission from Sm³⁺ has not been documented previously. The excitation spectrum of Eu³⁺ is dominated by a charge transfer band around 261 nm, and an additional band around 238 nm is always present, irrespective of the type of activator. The presence of this band for all these different types of activators was interpreted as host absorption.     

Luminescence properties of red‐emission Mg4Nb2O9:Eu3+ phosphor

Red‐emitting Mg₄Nb₂O₉:Eu³⁺ phosphor is synthesized via a solid‐state reaction method in air, and its crystal structure and luminescence are investigated. The phosphor can be excited efficiently by ~ 395 nm light, coupled well with a ~ 395 nm near‐ultraviolet chip and emits red light at ~ 613 nm with sharp spectra due to ⁵D₀ → ⁷ F₂ transition of the Eu³⁺ ion. Mg₄Nb₂O₉:Eu³⁺ phosphor sintered at 1350 ºC shows Commission international de I'Eclairage (CIE) chromaticity coordinates of x = 0.6354, y = 0.3592, and is a potential red‐emitting phosphor candidate for white light‐emitting diodes (W‐LEDs) under ~ 395 nm near‐ultraviolet LED chip excitation. Copyright © 2014 John Wiley & Sons, Ltd.     

Investigation on luminescence properties of Eu2+‐doped Ba3Al2O5Cl2 phosphor for near‐UV‐excited white LEDs

Ba₃Al₂O₅Cl₂:Eu²⁺ phosphor was prepared by combustion synthesis (CS). The prepared phosphor was excited at 329 nm; the phosphors shows an efficient bluish‐green wide‐band emission centred at 490 nm, which originates from the 4f⁶d¹ → 4f⁷ transition of Eu²⁺ ions. The excitation spectra of the phosphors have a band centred at 329 nm. It was also characterized by XRD, FT–IR for confirmation of phase purity, and FT–IR analysis indicated the vibrations of metal–oxygen (M–O) groups. SEM shows the morphology of the phosphor at the submicron scale. The results indicate that Ba₃Al₂O₅Cl₂:Eu²⁺ phosphor may be applicable for solid‐state lighting purposes. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and photoluminescence characteristics of Sm3+‐doped Bi4Si3O12 red‐emitting phosphor

A series of novel red‐emitting Sm³⁺‐doped bismuth silicate phosphors, Bi₄Si₃O₁₂:xSm³⁺ (0.01 ≤ x ≤ 0.06), were prepared via the sol–gel route. The phase of the synthesized samples calcinated at 800 °C is isostructural with Bi₄Si₃O₁₂ according to X‐ray diffraction results. Under excitation with 405 nm light, some typical peaks of Sm³⁺ ions centered at 566, 609, 655 and 715 nm are found in the emission spectra of the Sm³⁺‐doped Bi₄Si₃O₁₂ phosphors. The strongest peak located at 609 nm is due to ⁴G_5/2–⁶H_7/2 transition of Sm³⁺. The luminescence intensity reaches its maximum value when the Sm³⁺ ion content is 4 mol%. The results suggest that Bi₄Si₃O₁₂:Sm³⁺ may be a potential red phosphor for white light‐emitting diodes. Copyright © 2016 John Wiley & Sons, Ltd.     

Sol–gel preparation and luminescent properties of red‐emitting phosphor Sr‐Ba‐Mo‐W‐O‐(Eu3+,Sm3+)

Two series of red‐emitting phosphors Sr‐Ba‐Mo‐W‐O:Eu,Sm and Sr‐Ba‐Mo‐W‐O:Eu have been synthesized by a sol–gel method. The effects of the chemical composition, concentrations of Sm³⁺ and Eu³⁺, the Sr²⁺/Ba²⁺ ratio, and the W⁶⁺/Mo⁶⁺ ratio on the luminescent properties were investigated. The as‐prepared phosphors were characterized by X‐ray diffraction and Raman spectra. Results showed that single phases of the two series were prepared. The compositions of Sr_0.6Ba_0.13Mo_0.8 W_0.2O₄:Eu_0.10Sm_0.08 and Sr_0.75Ba_0.1Mo_0.8 W_0.2O₄:Eu_0.10 had the strongest luminescent intensity. The excitation spectra of Sm³⁺, Eu³⁺ co‐doped phosphors were broader and the strongest peak moved to 404 nm when compared with that of Eu³⁺ single‐doped phosphors. The luminescent intensity of the Sr_0.6Ba_0.13Mo_0.8 W_0.2O₄:Eu_0.10Sm_0.08 at 618 nm were 2.8 times greater than that of Sr_0.75Ba_0.1Mo_0.8 W_0.2O₄:Eu_0.10. The luminescent intensity of Sr_0.6Ba_0.13Mo_0.8 W_0.2O₄:Eu_0.10Sm_0.08 and Sr_0.75Ba_0.1Mo_0.8 W_0.2O₄:Eu_0.10 at 150 °C decreased to 56.8% and 50.3% of the initial value at room temperature, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Luminescent properties of novel red‐emitting M7Sn(PO4)6:Eu3+ (M = Sr,Ba) for light‐emitting diodes

Novel red‐emitting phosphors, Eu³⁺‐activated M₇Sn(PO₄)₆ (M = Sr, Ba), were synthesized at 1200°C by conventional solid‐state reaction method. The luminescent properties of M₇Sn(PO₄)₆:Eu³⁺ (M = Sr, Ba) phosphors were investigated, and the critical concentration of the activator (Eu³⁺) concentration were found to be 0.175 mol and 0.21 mol per formula unit for Sr_7‐xSn(PO₄)₆:xEu³⁺ and Ba_7‐xSn(PO₄)₆:xEu³⁺, respectively. These phosphors presented red luminescence under the excitation of 395 or 465 nm, perfectly matching with the emissions wavelength of near‐ultraviolet (UV) light‐emitting diodes (LEDs) and InGaN blue LED.     

Luminescent properties of sol–gel processed red‐emitting phosphor Ca0.6Sr0.4–1.5x‐0.5yMo0.4 W0.6O4:EuxLiy

A series of red‐emitting phosphors Ca_0.6Sr_{0.4–1.5x‐0.5y}Mo_0.4 W_0.6O₄:Eu_xLi_y (x = 0.02–0.12, y = 0–0.12) has been synthesized by a sol‐gel method. The effects of calcining temperature, concentrations of Li⁺ and Eu³⁺, and compensation ions on the luminescent properties were investigated. X‐ray diffraction and scanning electron microscopic results showed that as‐prepared phosphors were of single phase with several microns. The Li⁺ compensated compositions showed remarkably intense red emission at 619 nm. The emission intensity of the series reached maximum for compositions at x = 0.08 and y = 0.08 when the calcining temperature was 900 °C. Copyright © 2014 John Wiley & Sons, Ltd.