Luminescence of Eu and Ce in K3Ca2(SO4)3F fluoride material

A new halophosphor K₃Ca₂(SO₄)₃ F activated by Eu or Ce and K₃Ca₂(SO₄)₃ F:Ce,Eu co‐doped halosulfate phosphor has been synthesized by the co‐precipitation method and characterized for its photoluminescence (PL). The PL emission spectra of the K₃Ca₂(SO₄)₃ F :Ce phosphor show emission at 334 nm when excited at 278 nm due to 5d → 4f transition of Ce³⁺ ions. In the K₃Ca₂(SO₄)₃ F:Eu lattice, Eu²⁺ (440 nm) as well as Eu³⁺ (596 nm and 615 nm) emissions have been observed showing ⁵D₀ → ⁷ F₁ and ⁵D₀ → ⁷ F₂ transition of the Eu³⁺ ion, which is in the blue and red region of the visible spectrum respectively. The trivalent europium ion is very useful for studying the nature of metal coordination in various systems owing to its non‐degenerate emitting ⁵D₀ state. K₃Ca₂(SO₄)₃ F:Ce,Eu is suitable for Ce³⁺ → Eu²⁺ → Eu³⁺ energy transfer in which Ce³⁺and Eu²⁺ play the role of sensitizers and Eu²⁺ and Eu³⁺ act as the activators. The observations presented in this paper are relevant for lamp phosphors. Copyright © 2015 John Wiley & Sons, Ltd.     

Photoluminescence enhancement in Na3SO4Cl:X (X = Ce3+, Eu3+ or Dy3+) material

The compound Na₃SO₄Cl X (X = Ce³⁺, Eu³⁺ or Dy³⁺) prepared by the wet chemical method was studied for its photoluminescence (PL) and energy transfer characteristics. The PL from Na₃SO₄Cl:Ce³⁺ shows strong emission at 322 nm at an excitation of 272 nm. Therefore, an efficient Ce³⁺ → Dy³⁺, Eu²⁺ → Dy³⁺ and Eu²⁺ → Eu³⁺ energy transfer had taken place in this host. The Dy³⁺ emission caused by Ce³⁺ → Dy³⁺ energy transfer under ultraviolet (UV) wavelengths peaked at around 477 nm and 572 nm due to ⁴ F_9/2 → ⁶H_15/2 and ⁶H_13/2 transitions with yellow–orange emission in the Na₃SO₄Cl lattice. An intense Dy³⁺ emission was observed at 482 and 576 nm caused by the Eu²⁺ → Dy³⁺ energy transfer process and due to ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions respectively. The Eu³⁺ blue to red light emission caused by the Eu²⁺ → Eu³⁺ energy transfer peaked at 593 nm and 617 nm due to ⁵D₀ → ⁵D₃ transitions. The presence of trivalent Eu in Na₃SO₄Cl suggested the presence of Eu³⁺ in the host compound that occupied two different lattice sites and that peaked at 593 and 617 nm due to ⁵D₀ → ⁷ F₁ and ⁵D₀ → ⁷ F₂ transitions respectively. The trivalent europium ion is very useful for studying the nature of metal coordination in various systems due to its non‐degenerate emitting ⁵D₀ state. The present paper discusses the photoluminescence characteristics of Eu²⁺ → Dy³⁺ and Eu²⁺ → Eu³⁺ energy transfer. This compound may be useful as a lamp phosphor. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of Dy3+ or Eu2+ co‐activator on a BaCa(SO4)2:Ce3+ mixed alkaline earth sulfate phosphor

The individual emission and energy transfer between Ce³⁺ and Eu²⁺ or Dy³⁺ in BaCa(SO₄)₂ mixed alkaline earth sulfate phosphor prepared using a co‐precipitation method is described. The phosphor was characterized by X‐ray diffraction (XRD) and photoluminescence (PL) studies and doped by Ce;Eu and Dy rare earths. All phosphors showed excellent blue–orange emission on excitation with UV light. PL measurements reveal that the emission intensity of Eu²⁺ or Dy³⁺ dopants is greater than when they are co‐doped with Ce³⁺. An efficient Ce³⁺ → Eu²⁺ [²T_2g(4f⁶5d) → ⁸S_7/2(4f₇)] and Ce³⁺ → Dy³⁺ (⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2) energy transfer takes place in the BaCa(SO₄)₂ host. A strong blue emission peak was observed at 462 nm for Eu²⁺ ions and an orange emission peak at 574 nm for Dy³⁺ ions. Hence, this phosphor may be used as a lamp phosphor. Copyright © 2015 John Wiley & Sons, Ltd.     

Impact of temperature on Na2Sr(PO4)F:Eu3+ phosphor

In this article, we report the synthesis of Na₂Sr_1‐x(PO₄)F:Eu_x phosphor via a combustion method. The influence of different annealing temperatures on the photoluminescence properties was investigated. The phosphor was excited at both 254 and 393 nm. Na₂Sr_1‐x(PO₄)F:Eu_x³⁺ phosphors emit strong orange and red color at 593 and 612 nm, respectively, under both excitation wavelengths. Na₂Sr_1‐x(PO₄)F:Eu_x³⁺ phosphors annealed at 1050°C showed stronger emission intensity compared with 600, 900 and 1200°C. Moreover, Na₂Sr_1‐x(PO₄)F:Eu_x³⁺ phosphor was found to be more intense when compared with commercial Y₂O₃:Eu³⁺ phosphor. Copyright © 2013 John Wiley & Sons, Ltd.     

Dy(3+) and Mn(2+) emission in fluoride- and chloride-based Na(3) (SO(4) )X (X = F or Cl) phosphors

In the present study, Na₃(SO₄)X (X = F or Cl) halosulphate phosphors have been synthesized by the solid‐state diffusion method. The phase formation of the compounds Na₃(SO₄)F and Na₃(SO₄)Cl were confirmed by X‐ray powder diffraction (XRD) measurement. Photoluminescence (PL) excitation spectrum measurement of Na₃(SO₄)F:Ce³⁺ and Na₃(SO₄)Cl:Ce³⁺ shows this phosphor can be efficiently excited by near‐ultraviolet (UV) light and presents a dominant luminescence band centred at 341 nm for Ce³⁺, which is responsible for energy transfer to Dy³⁺and Mn²⁺ ions. The efficient Ce³⁺ → Dy³⁺ energy transfer in Na₃(SO₄)F and Na₃(SO₄)Cl under UV wavelength was observed due to ⁴ F_9/2 to ⁶H_15/2 and ⁶H_13/2 level, while Ce³⁺ → Mn²⁺ was observed due to ⁴ T₁ state to ⁶A₁. The purpose of the present study is to develop and understanding the photoluminescence properties of Ce³⁺‐, Dy³⁺‐ and Mn²⁺‐doped fluoride and chloride Na₃(SO₄)X (X = F or Cl) luminescent material, which can be the efficient phosphors in many applications, such as scintillation applications, TL dosimetry and the lamp industry, etc. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Synthesis and characterization of novel Na15(SO4)5F4Cl:Ce3+ halosulfate phosphors

A series of Na₁₅(SO₄)₅F₄Cl phosphors doped with Ce³⁺ ions was prepared using the wet chemical method. X‐Ray diffraction studies were used to determine their phase formation and purity. Fourier transform infrared spectroscopy effectively identified the chemical bonds present in the molecule. The photoluminescence properties of the as‐prepared phosphors were investigated and the Ce³⁺ ions in these hosts were found to give broadband emission in the UV range. For the thermoluminescence study, phosphors were irradiated with a 5 Gy dose of γ‐rays from a ⁶⁰Co source. Chen’s half‐width method was employed to calculate the trapping parameters from the thermoluminescence glow curve. Copyright © 2016 John Wiley & Sons, Ltd.     

Optical properties and energy transfer of Eu2+/Ce3+ co‐activated Na3Ca6(PO4)5 phosphor

Ce³⁺/Eu²⁺ co‐doped Na₃Ca₆(PO₄)₅ phosphors were prepared using a combustion‐assisted synthesis method. X‐Ray powder diffraction (XRD) analysis confirmed the formation of a Na₃Ca₆(PO₄)₅ crystal phase. Na₃Ca₆(PO₄)₅:Eu²⁺ phosphors have an efficient bluish‐green emission band that peaks at 489 nm, whereas Ce³⁺‐doped Na₃Ca₆(PO₄)₅ showed a bright emission band at 391 nm. Analysis of the experimental results suggests that enhancement of the Eu²⁺ emission intensity in co‐doped Na₃Ca₆(PO₄)₅:Eu²⁺,Ce³⁺ phosphors is due to a resonance‐type energy transfer from Ce³⁺ to Eu²⁺ ions, which is predominantly governed by an exchange interaction mechanism. These results indicate that Ce³⁺/Eu²⁺ co‐doped Na₃Ca₆(PO₄)₅ is potentially useful as a highly efficient, bluish‐green emitting, UV‐convertible phosphor for white‐light‐emitting diodes. Copyright © 2014 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 in Li3Al2(PO4)3:Eu2+

A series of efficient Li₃Al₂(PO₄)₃:Eu²⁺ novel phosphors were synthesized by the facile combustion method. The effects of dopant on the luminescence behavior of Li₃Al₂(PO₄)₃ phosphor were also investigated. The phosphors were characterized by X‐ray diffraction, field emission scanning electron microscope and photoluminescence techniques. The result shows that all samples can be excited efficiently by near‐ultraviolet excitation under 310 nm. The emission was observed for Li₃Al₂(PO₄)₃:Eu²⁺ phosphor at 425 nm, which corresponded to the d → f transition. The concentration quenching of Eu²⁺ was observed in Li₃Al₂(PO₄)₃:Eu²⁺ when the Eu concentration was at 0.5 mol%. The prepared powders exhibited intense blue emission at the 425 nm owing to the Eu²⁺ ion by Hg‐free excitation at 310 nm (i.e., solid‐state lighting excitation). Consequently, the availability of such a phosphor will significantly help in the development of blue‐emitting solid‐state lighting applications. Copyright © 2012 John Wiley & Sons, Ltd.     

Resonant and non‐resonant energy transfer from Ce3+ → X (X = Tb3+, Eu3+ or Dy3+) in NaMgSO4F material

An inorganic NaMgSO₄F fluoride material was prepared by the wet chemical method and studied for its photoluminescence (PL) and resonant–non‐resonant energy transfer (RET and NORET) capabilities between Ce³⁺ → Tb³⁺, Ce³⁺ → Eu³⁺ and Ce³⁺ → Dy³⁺ rare earth ions. The Tb³⁺ emission for Ce³⁺ → Tb³⁺ transfers under ultraviolet (UV) wavelengths peaked at 491, 547, and 586 nm, for excitation at 308 nm due to ⁵D₄ → ⁷F_J (J = 4, 5, 6) transitions. Eu emission spectra were observed at 440 nm (Eu²⁺), 593 nm and 616 nm (Eu³⁺) recorded for different concentrations of materials, whereas Dy³⁺ emission from Ce³⁺ → Dy³⁺ transfer under UV wavelengths peaked at 485 nm and 577 nm due to ⁴F_9/2 → ⁶H_15/2 and ⁶H_13/2 transitions. The purpose of the present study is to understand the RET and NORET effects of Tb³⁺, Eu³⁺ and Dy³⁺ co‐doping in a NaMgSO₄F:Ce³⁺ luminescent material, which could be used as a green‐emitting material for lamp phosphors.     

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.     

Effect of temperature on intense green emitting Na2Ca(PO4)F:Mn2+ phosphor

An intense green luminescent Na₂Ca(PO₄)F:Mn²⁺ phosphor has been prepared at high temperature by reduction treatment in a charcoal environment. The emission band of Mn²⁺ was obtained at around 522 nm (green) under 259 nm excitation. Enhancement in emission intensity arising from the thermal treatment is reported. The intense emission of the spectrum was assigned to electronic transitions ⁴T₁ → ⁶A₁ of Mn²⁺ ions. Intense PL emission suggested that temperature employed plays an important role in the present matrix. X‐ray diffraction pattern, photoluminescence and morphology by SEM of the host lattice of phosphors at different temperatures have been reported in this paper. The results obtained show that the present phosphor has potential for application in green emitting phosphors for the lamp industry. Copyright © 2010 John Wiley & Sons, Ltd.     

Luminescence characterization of Dy and Eu doped Na6Mg(SO4)4 phosphors

A series of single‐phase phosphors based on Na₆Mg(SO₄)₄ (Z_eff = 11.70) doped with Dy and Eu was prepared by the wet chemical method. The photoluminescence (PL) and thermoluminescence (TL) properties of Dy³⁺‐ and Eu³⁺‐activated Na₆Mg(SO₄)₄ phosphors were investigated. The characteristic emissions of Dy³⁺ and Eu³⁺ were observed in the Na₆Mg(SO₄)₄ host. The TL glow curve of the Na₆Mg(SO₄)₄:Dy phosphor consisted of a prominent peak at 234°C and a very small hump at 158°C. The TL sensitivity of the Na₆Mg(SO₄)₄:Dy phosphor was found to be four times less than the commercialized CaSO₄:Dy phosphor. The TL dose–response of the Na₆Mg(SO₄)₄:Dy phosphor was studied from a dose range of 5–10 kGy and the linear dose–response was observed up to 1 kGy which is good for a microcrystalline phosphor. Trapping parameters for both the samples were calculated using the Initial Rise and Chen's peak shape methods.     

Luminescence properties of Ce3+ in orthosilicate oxyapatite NaY9(SiO4)6O2

Ce³⁺‐doped orthosilicate oxyapatite NaY₉(SiO₄)₆O₂ phosphors NaY_9–x(SiO₄)₆O₂:xCe³⁺ were prepared by a conventional high‐temperature solid‐state reaction method, and their spectroscopic characteristics were systematically investigated. The occupancies of Ce³⁺ ions at two different sites (Wyckoff 6 h and 4f sites) in NaY₉(SiO₄)₆O₂ were determined. The influence of doping concentration on the emission intensity of Ce³⁺ was investigated and the critical distance Rc was estimated in terms of the concentration quenching data.     

Dy3+‐, Sm3+‐, Ce3+‐ and Tb3+‐activated optical properties of microcrystalline BaMgP2O7 phosphors

Photoluminescence (PL) and thermoluminescence (TL) properties of rare earth (RE) ion (RE = Dy³⁺, Sm³⁺, Ce³⁺, Tb³⁺) activated microcrystalline BaMgP₂O₇ phosphors are presented in this work. Non‐doped and doped samples of BaMgP₂O₇ were prepared using a solid state diffusion method and characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), PL and TL. The XRD measurement confirmed the phase purity of the BaMgP₂O₇ host matrix. The average particle size was found through SEM measurement to be around 2 μm. All activators using the PL technique displayed characteristic excitation and emission spectra that corresponded to their typical f → f and f → d transitions respectively. Thermoluminescence measurements showed that BaMgP₂O₇:RE (RE = Dy³⁺, Sm³⁺, Tb³⁺, Ce³⁺) and co‐doped BaMgP₂O₇:Ce³⁺,Tb³⁺ phosphors have also TL behaviour.     

Green‐light emission through energy transfer from Ce3+ to Tb3+ ions in the Li2SO4–Al2(SO4)3 system

An energy transfer process from Ce³⁺ to Tb³⁺ ions was successfully achieved in a Li₂SO₄–Al₂(SO₄)₃ mixed‐sulphate system. A wet‐chemical synthesis was employed to prepare the Li₂SO₄–Al₂(SO₄)₃ system by doping Ce³⁺ and Tb³⁺ ions individually as well as collectively. The phases were identified using X‐ray diffraction studies. The as‐prepared samples were characterized by FT‐IR and photoluminescence measurements. Green‐light emission was exhibited by Ce³⁺, Tb³⁺ co‐doped Li₂SO₄–Al₂(SO₄)₃ system, thus, indicating its potential as a material for display devices or in the lamp industry.     

Upconverted photoluminescence in Ho3+ and Yb3+ codoped Gd2O3 nanocrystals with and without Li+ ions

The upconversion photoluminescence of Ho³⁺ ion sensitized by Yb³⁺ ion in Ho³⁺/Yb³⁺codoped Gd₂O₃ nanocrystals with and without Li⁺ is investigated in this paper. Strong fluorescence in the green (534–570 nm) and red (635–674 nm) regions of the spectrum has been observed, arising from the ⁵F₄/⁵S₂ → ⁵I₈ and ⁵F₅ → ⁵I₈ transitions of Ho³⁺ ion, respectively. Yb³⁺ ion is considered to be a better sensitizer for catching enough pumping energy and transferring considerable energy to Ho³⁺ in the Ho³⁺/Yb³⁺system. The upconversion intensity emitted by Ho³⁺ is greatly enhanced when Li⁺ is added to the Ho³⁺/Yb³⁺ codoped Gd₂O₃ nanocrystals.     

Enhanced red emission from BaMoO4: Eu3+ by Bi3+ co‐doping

A series of Bi³⁺,Eu³⁺‐doped BaMoO₄ phosphors was synthesized using a hydrothermal method. The crystal structure, morphology and optical properties of the phosphors were studied using X‐ray diffraction (XRD), scanning electron microscope (SEM) and photoluminescence (PL) measurements. Three different particle morphologies were detected in the SEM observation. The energy dispersive spectroscopy (EDS) results indicated that the solubility of Bi³⁺ in spherical or rugby‐like BaMoO₄ particles was very low and the excess Bi³⁺ element was cumulated in the irregular particles. Characteristic emissions of Eu³⁺ ions (⁵D₀ → ⁷F_J; J = 0, 1, 2, 3, 4) were observed under excitation in ultraviolet (UV) light, with the most intense transition being the ⁵D₀ → ⁷F₂ transition. Energy transfer from MoO₄^2? and Bi³⁺ to Eu³⁺ can be readily achieved. Red emission intensity of Eu³⁺ was enhanced by a factor of two by co‐doping with a small amount of Bi³⁺. Optical properties as a function of Bi³⁺ content were studied and the optimum Bi³⁺ content in BaMoO₄ nanocrystals was determined to be 0.4 mol%.     

Energy transfer in M5(PO4)3 F:Eu2+,Ce3+ (M = Ca and Ba) phosphors

M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) co‐doped with Ce³⁺ phosphors were successfully prepared by the combustion synthesis method. The introduction of co‐dopant (Ce³⁺) into the host enhanced the luminescent intensity of the M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) efficiently. Previously, we have reported the synthesis and photoluminescence properties of same phosphors. The aim of this article is to report energy transfer mechanism between Ce³⁺?Eu²⁺ ions in M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) phosphors, where Ce³⁺ ions act as sensitizers and Eu²⁺ ions act as activators. The M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) co‐doped with Ce³⁺ phosphor exhibits great potential for use in white ultraviolet (UV) light‐emitting diode applications to serve as a single‐phased phosphor that can be pumped with near‐UV or UV light‐emitting diodes. Copyright © 2013 John Wiley & Sons, Ltd.