Luminescence and spectroscopic studies of halosulfate phosphors: a review

This review discusses the photoluminescence (PL) characteristics of halosulfate phosphors developed by us. Halosulfate phosphors KCaSO₄Cl:X,Y (X = Eu or Ce; Y = Dy or Mn) and Na₆(SO₄)₂FCl (doped with Dy, Ce or Eu) were prepared using a solid‐state diffusion method. The mechanism of energy transfer from Eu²⁺→Dy³⁺, Ce³⁺→Dy³⁺ and Ce³⁺→Mn²⁺ has also been studied. Dy³⁺ emission in the host at 475 and 570 nm is observed due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transition, whereas the PL emission spectra of Na₆(SO₄)₂FCl:Ce phosphor shows Ce³⁺ emission at 322 nm due to 5d→4f transition of the Ce³⁺ ion. The main property of KCaSO₄Cl is its very high sensitivity, particularly when doped by Dy, Mn or Pb activators. This review also discusses the PL characteristics of some new phosphors such as LiMgSO₄F, Na₆Pb₄(SO₄)₆Cl₂, Na₂₁Mg(SO₄)₁₀Cl₃ and Na₁₅(SO₄)₅F₄Cl. Copyright © 2014 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.     

Enhanced luminescence and white light emission from Eu3+‐co‐doped K3Ca2(SO4)3Cl:Dy3+ phosphor with near visible ultraviolet excitation for white LEDs

The luminescent properties of europium (Eu)‐ and dysprosium (Dy)‐co‐doped K₃Ca₂(SO₄)₃Cl halosulfate phosphors were analyzed. This paper reports the photoluminescence (PL) properties of K₃Ca₂(SO₄)₃Cl microphosphor doped with Eu and Dy and synthesized using a cost‐effective wet chemical method. The phosphors were characterized by X‐ray diffraction and scanning electron microscopy. The CIE coordinates were calculated to display the color of the phosphor. PL emission of the prepared samples show peaks at 484 nm (blue), 575 nm (yellow), 594 nm (orange) and 617 nm (red). The emission color of the Eu,Dy‐co‐doped K₃Ca₂(SO₄)₃Cl halophosphor depends on the doping concentration and excitation wavelength. The addition of Eu in K₃Ca₂(SO₄)₃Cl:Dy greatly enhances the intensity of the blue and yellow peaks, which corresponds to the ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions (under 351 nm excitation). The Eu³⁺/Dy³⁺ co‐doping also produces white light emission for 1 mol% of Eu³⁺, 1 mol% of Dy³⁺ in the K₃Ca₂(SO₄)₃Cl lattice under 396 nm excitation, for which the calculated chromaticity coordinates are (0.35, 0.31). Thus, K₃Ca₂(SO₄)₃Cl co‐doped with Eu/Dy is a suitable candidate for NUV based white light‐emitting phosphors technology. Copyright © 2014 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.     

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.     

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.     

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.     

Optical properties of CaAl(SO4)2Br:RE (RE = Dy,Eu, Ce) novel phosphors

A new phosphor CaAl(SO₄)₂Br doped with Dy, Ce and Eu is reported. Rare earth (Dy, Eu and Ce)‐doped polycrystalline CaAl(SO₄)₂Br phosphors were prepared using a wet chemical reaction method and studied for X‐ray diffraction and photoluminescence (PL) characteristics. Dy³⁺ emission in the CaAl(SO₄)₂Br lattice was observed at 484 and 574 nm in the blue and yellow regions of the spectrum, which are assigned to ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of the Dy³⁺ ion, respectively. While the PL emission spectra of CaAl(SO₄)₂Br:Ce phosphor showed Ce³⁺ emission at 347 nm due to 5d → 4f transition of the Ce³⁺ ion. In a CaAl(SO₄)₂Br:Eu lattice, Eu³⁺ emissions were observed at 593 and 617 nm, coming from the ⁵D₀ → ⁷ F₁ and ⁵D₀ → ⁷ F₂ electron transitions, respectively. The PL study showed that the intensity of electric dipole transition at 617 nm dominates over that of magnetic dipole transition at 590 nm. The maximum PL intensity was obtained for a 1 mol% concentration of Eu³⁺ in CaAl(SO₄)₂Br host lattice. The results showed that the material may be a promising candidate as a blue‐, yellow‐ and red‐emitting phosphor. Copyright © 2013 John Wiley & Sons, Ltd.     

Combustion synthesis of Na2Sr(PO4)F:Dy3+ white light emitting phosphor

The synthesis, X‐ray diffraction, photoluminescence, TGA/DTA and FTIR techniques in Dy³⁺ activated Na₂Sr(PO₄)F phosphor are reported in this paper. The prepared phosphor gave blue, yellow and red emission in the visible region of the spectrum at 348 nm excitation. CIE color co‐ordinates of Na₂Sr(PO₄)F:Dy³⁺ are suitable as white light‐emitting phosphors. Copyright © 2009 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.     

Dual emission of Ce3+,Mn2+‐coactivated Ca3YNa(PO4)3F via energy transfer: a single component white/yellow‐emitting phosphor

A series of Ce³⁺,Mn²⁺‐coactivated Ca₃YNa(PO₄)₃F phosphors were synthesized via a traditional solid‐state reaction under a reductive atmosphere. X‐Ray powder diffraction was used to confirm that the crystal structure and diffraction peaks of Ce³⁺/Mn²⁺‐doped samples matched well with the standard data. A spectral overlap between the emission band of Ce³⁺ and the excitation band of Mn²⁺ suggested the occurrence of energy transfer from Ce³⁺ to Mn²⁺. With increasing Mn²⁺ content, the emission intensities and lifetime values of the Ce³⁺ emission for Ca₃YNa(PO₄)₃F:Ce³⁺,Mn²⁺ phosphors linearly decrease, whereas the energy transfer efficiencies gradually increase to 89.35%. By adjusting the relative concentrations of Ce³⁺ and Mn²⁺, the emission hues are tuned from blue to white and eventually to yellow. These results suggest that Ca₃YNa(PO₄)₃F:Ce³⁺,Mn²⁺ phosphors have promising application as white‐emitting phosphors for near‐ultraviolet light‐emitting diodes.     

Synthesis and photoluminescence characteristics of (Y,Gd)BO3:RE (RE = Eu3+, Ce3+, Dy3+ and Tb3+) phosphors for blue chip and near‐UV white LEDs

A series of Eu³⁺‐, Ce³⁺‐, Dy³⁺‐ and Tb³⁺‐doped (Y,Gd)BO₃ phosphors was synthesized by a solid‐state diffusion method. X‐Ray diffraction confirmed their hexagonal structure and the scanning electron microscopy results showed crystalline particles. The excitation spectra revealed that (Y,Gd)BO₃ phosphors doped with Eu³⁺, Ce³⁺ , Dy³⁺ and Tb³⁺ are effectively excited with near UV‐light of 395 nm/blue light, 364, 351 and 314 nm, respectively. Photoluminescence spectra of Eu³⁺‐, Ce³⁺‐ and Tb³⁺/Dy³⁺‐doped phosphor showed intense emission of reddish orange, blue and white light, respectively. The phosphor Y_0.60Gd_0.38BO₃:Ce_0.02 showed CIE 1931 color coordinates of (0.158, 0.031) and better color purity compared with commercially available blue BAM:Eu²⁺ phosphor. The phosphor (Y,Gd)BO₃ doped with Eu³⁺, Dy³⁺ and Tb³⁺ showed CIE 1931 color coordinates of (0.667, 0.332), (0.251, 0.299) and (0.333, 0.391) respectively. Significant photoluminescence characteristics of the prepared phosphors indicate that they might serve as potential candidates for blue chip and near‐UV white light‐emitting diode applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Luminescence characteristics of Na3Ca2(SO4)3F: Ce3+ fluoride material

A new Na₃Ca₂(SO₄)₃F: Ce³⁺ phosphor synthesized by a solid state diffusion method is reported. The photoluminescence study showed a single high intensity emission peak at 307 nm wavelength when excited by UV light of wavelength 278 nm. An unresolved peak of comparatively less intensity was also observed at 357 nm along with the main peak. The characteristic emission of dopant Ce in Na₃Ca₂(SO₄)₃F phosphor clearly indicated that it resides in the host lattice in trivalent form. The emission peak can be attributed to 5d → 4f transition of rare earth Ce³⁺. The prepared sample is also characterized for its thermoluminescence properties. The TL glow curve of prepared sample showed a single broad peak at 147°C. The trapping parameters are also evaluated by Chen's method. The values of trap depth (E) and frequency factor (s) were found to be 0.64 ± 0.002 eV and 1.43 × 10⁷ s^–1 respectively. The study of PL and TL along with evaluation of trapping parameters has been undertaken and discussed for the first time. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and characterization of KCe(PO3)4 doped with some lanthanide activators

KCe(PO₃)₄ doped with Dy³⁺,Tb³⁺,Yb³⁺and Nd³⁺ phosphors were synthesized by a solid state diffusion method. The prepared samples were characterized by X‐ray diffraction and photoluminescence. KCe(PO₃)₄ exhibits emission in ultraviolet (UV) region which indicates weak Ce³⁺–Ce³⁺ interaction. The Ce³⁺–Ce³⁺energy transfer is not efficient. In light of this, energy transfer from Ce³⁺ to other lanthanides like Dy³⁺, Tb³⁺,Yb³⁺ and Nd³⁺ is rather surprising.     

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.     

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.     

Photoluminescence properties and energy transfer in Ce3+/Dy3+ co‐doped Sr3MgSi2O8 phosphors for potential application in ultraviolet white light‐emitting diodes

Sr₃MgSi₂O₈:Ce³⁺, Dy³⁺ phosphors were prepared by a solid‐state reaction technique and the photoluminescence properties were investigated. The emission spectra show not only a band due to Ce³⁺ ions (403 nm) but also as a band due to Dy³⁺ ions (480, 575 nm) (UV light excitation). The photoluminescence properties reveal that effective energy transfer occurs in Ce³⁺/Dy³⁺ co‐doped Sr₃MgSi₂O₈ phosphors, and the co‐doping of Ce³⁺ could enhance the emission intensity of Dy³⁺ to a certain extent by transferring its energy to Dy³⁺. The Ce³⁺/Dy³⁺ energy transfer was investigated by emission/excitation spectra, and photoluminescence decay behaviors. In Sr_2.94MgSi₂O₈:0.01Ce³⁺, 0.05Dy³⁺ phosphors, the fluorescence lifetime of Dy³⁺ (from 3.35 to 27.59 ns) is increased whereas that of Ce³⁺ is greatly decreased (from 43.59 to 13.55 ns), and this provides indirect evidence of the Ce³⁺ to Dy³⁺ energy transfer. The varied emitted color of Sr₃MgSi₂O₈:Ce³⁺, Dy³⁺ phosphors from blue to white were achieved by altering the concentration ratio of Ce³⁺ and Dy³⁺. These results indicate Sr₃MgSi₂O₈:Ce³⁺, Dy³⁺ may be as a candidate phosphor for white light‐emitting diodes. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhancement of the luminescence properties of Sr3(PO4)2:Dy3+,Li+ white‐light‐emitting phosphors by charge compensator Li+ co‐doping

Sr₃(PO₄)₂:Dy³⁺,Li⁺ phosphors were prepared using a simple high temperature solid method for luminescence enhancement. The structures of the as‐prepared samples agreed well with the standard phase of Sr₃(PO₄)₂, even when Dy³⁺ and Li⁺ were introduced. Under ultraviolet excitation at 350 nm, the Sr₃(PO₄)₂:Dy³⁺ sample exhibited two emission peaks at 483 nm and 580 nm, which were due to the ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions, respectively. A white light was fabricated using these two emissions from the Sr₃(PO₄)₂:Dy³⁺ phosphors. The luminescence properties of Sr₃(PO₄)₂:Dy³⁺,Li⁺ phosphors, including emission intensity and decay time, were improved remarkably with the addition of Li⁺ as the charge compensator, which would promote their application in near‐ultraviolet excited white‐light‐emitting diodes.     

Dy3+‐activated NaM4 (VO4)3 (M = Ca,Ba, Sr) phosphor for near‐UV solid‐state lighting

We report the photoluminescence characterization of Dy³⁺‐activated NaM₄(VO₄)₃ (M = Ca, Ba, Sr) phosphors prepared by a solid‐state method. The synthesis was confirmed by X‐ray diffraction (XRD) characterization and photoluminescence (PL) emission results showed sharp blue and yellow bands for NaM₄(VO₄)₃ (M = Ca, Ba, Sr):Dy³⁺ phosphors at the excitation wavelength of 323 nm, which is near‐UV excitation. Thus, these phosphors could be applicable for near‐UV excited solid‐state lighting devices. Copyright © 2011 John Wiley & Sons, Ltd.