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.     

Luminescent properties of Ca3SiO4Cl2 co‐doped with Ce3+ and Eu2+ for near‐ultraviolet light‐emitting diodes

Ca₃SiO₄Cl₂ co‐doped with Ce³⁺,Eu²⁺ was prepared by high temperature reaction. The structure, luminescent properties and the energy transfer process of Ca₃SiO₄Cl₂: Ce³⁺,Eu²⁺ were investigated. Eu²⁺ ions can give enhanced green emission through Ce³⁺ → Eu²⁺ energy transfer in these phosphors. The green phosphor Ca_2.9775SiO₄Cl₂:0.0045Ce³⁺,0.018Eu²⁺ showed intense green emission with broader excitation in the near‐ultraviolet light range. A green light‐emitting diode (LED) based on this phosphor was made, and bright green light from this green LED could be observed by the naked eye under 20 mA current excitation. Hence it is considered to be a good candidate for the green component of a three‐band white LED. Copyright © 2015 John Wiley & Sons, Ltd.     

Photoluminescence properties of LiBaPO4:M3+ phosphor for near‐UV light‐emitting diode (M = Eu and Dy)

A novel phosphor LiBaPO₄ doped with rare earths Eu and Dy prepared by high temperature solid‐state reaction method is reported. The phosphors were characterized by X‐ray powder diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL). The emission and excitation spectra of these materials were measured at room temperature with a spectrofluorophotometer. The excitation spectra of LiBaPO₄:Eu³⁺ phosphor can be efficiently excited by 394 nm, which is matched well with the emission wavelength of near‐UV light‐emitting diode (LED) chip. PL properties of Eu³⁺‐doped LiBaPO₄ exhibited the characteristic red emission coming from ⁵D₀ → ⁷ F₁ (593 nm) and ⁵D₀ → ⁷ F₂ (617 nm) electronic transitions with color co‐ordinations of (0.680, 0.315). The results demonstrated that LiBaPO₄:Eu³⁺ is a potential red‐emitting phosphor for near‐UV LEDs. Emission spectra of LiBaPO₄:Dy³⁺ phosphors showed efficient blue (481 nm) and yellow (574 nm) bands, which originated from ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of the Dy³⁺ ion, respectively. The 574 nm line is more intense than the 481 nm lines, which indicates that the site Dy³⁺ is located with low symmetry. This article summarizes fundamentals and possible applications of optically useful inorganic phosphates with visible photoluminescence of Eu³⁺ and Dy³⁺ ions. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

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.     

Wet‐chemical preparation of Ce3+‐activated K2LaX5 (X = Cl,Br or I) phosphors

There has been a renewed interest in Ce³⁺‐activated halide phosphors due to applications as scintillation detectors, especially for positron emission tomography. For K₂LaCl₅, the light yield increases and the energy resolution (FWHM) improves with increasing Ce³⁺ doping. K₂LaX₅ compounds are also important as laser hosts for the mid‐IR range. K₂LaCl₅:Nd crystals show bright mid‐IR luminescence, which makes them a candidate for IR laser materials. Efficient emission in the IR range has also been reported in K₂LaCl₅:U³⁺. A one‐step, wet chemical process for preparing Ce³⁺‐activated K₂LaCl₅ phosphor is described. Intense luminescence of Ce³⁺ can be observed in the as‐prepared powders without any heat treatment. The availability of such powders opens up several exciting possibilities, such as growing single crystals without going to the high temperatures required for melting the constituent chlorides, or even obtaining processed, transparent, Ce³⁺‐activated materials without taking recourse to crystal growth. Copyright © 2011 John Wiley & Sons, Ltd.     

Luminescence enhancement of (Sr1–xMx)2SiO4:Eu2+ phosphors with M (Ca2+/Zn2+) partial substitution for white light‐emitting diodes

Eu²⁺‐doped Sr₂SiO₄ phosphor with Ca²⁺/Zn²⁺ substitution, (Sr_1–xM_x)₂SiO₄:Eu²⁺ (M = Ca, Zn), was prepared using a high‐temperature solid‐state reaction method. The structure and luminescence properties of Ca²⁺/Zn²⁺ partially substituted Sr₂SiO₄:Eu²⁺ phosphors were investigated in detail. With Ca²⁺ or Zn²⁺ added to the silicate host, the crystal phase could be transformed between the α‐form and the β‐form of the Sr₂SiO₄ structure. Under UV excitation at 367 nm, all samples exhibit a broad band emission from 420 to 680 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions. The broad emission band consists of two peaks at 482 and 547 nm, which correspond to Eu²⁺ ions occupying the ten‐fold oxygen‐coordinated Sr.(I) site and the nine‐fold oxygen‐coordinated Sr.(II) site, respectively. The luminescence properties, including the intensity and lifetime of Sr₂SiO₄:Eu²⁺ phosphors, improved remarkably on Ca²⁺/Zn²⁺ addition, and promote its application in white light‐emitting diodes. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of Mg doping in Sr2SiO4:Eu2+ nanophosphors for blue and white emission at near‐UV excitation

Nanophosphors of (Sr_0.98‐xMg_xEu_0.02)₂SiO₄ (x = 0, 0.18, 0.38, 0.58 and 0.78) were prepared through low temperature solution combustion method and their luminescence properties were studied. The emission peak for Eu²⁺ ?doped Sr₂SiO₄ nanophosphor is observed at ~490 nm and ~553 nm corresponding to two Sr²⁺ sites Sr(I) and Sr(II) respectively for 395 nm excitation. However the addition of Mg²⁺ dopant in Sr₂SiO₄ leads to suppression of ~553 nm emission peak due to absence of energy levels of Sr (II) sites which results in a single broad emission at ~460 nm. It was shown that the emission peak blue shifted with increase in Mg concentration which may be attributed to change in crystal field environment around Sr(I) sites. Therefore, the (Mg_0.78Sr_0.20Eu_0.02)₂SiO₄ nanophosphor can be used for blue emission and the Sr₂SiO₄:Eu_0.04²⁺ for green–yellow emission at 395 nm excitations. The Commission International de L'Eclairage (CIE) chromaticity coordinates for mixed powders of (Mg_0.78Sr_0.20Eu_0.02)₂SiO₄ and Sr₂SiO₄:Eu_0.04²⁺ (in a 1:1 ratio) fall in the white region demonstrating the possible use of the mixture in white light generation using near‐UV excitation source.     

Novel red colour emitting Ca0.995Mg2(SO4)3:0.5Eu2+ phosphor under ultraviolet,blue, and green excitation for plant growth LEDs

In the recent few years, Eu²⁺- and Mn⁴⁺-activated phosphors are widely used as potential colour converters for indoor plant cultivation lighting application due to their marvellous luminescence characteristics as well as low cost. In this investigation, we synthesized novel red colour-emitting Ca_(2−x)Mg₂(SO₄)₃:xmol% Eu²⁺ (x = 0–1.0 mol%) phosphors via a solid-state reaction method in a reducing atmosphere. The photoluminescence (PL) excitation spectra of synthesized phosphors exhibited a broad excitation band with three excitation bands peaking at 349 nm, 494 nm, and 554 nm. Under these excitations, emission spectra exhibited a broad band in the red colour region at ~634 nm. The PL emission intensity was measured for different concentrations of Eu²⁺. The maximum Eu²⁺ doping concentration in the Ca₂Mg₂(SO₄)₃ host was observed for 0.5 mol%. According to Dexter theory, it was determined that dipole–dipole interaction was responsible for the concentration quenching. The luminous red colour emission of the sample was confirmed using Commission international de l'eclairage colour coordinates. The results of PL excitation and emission spectra of the prepared phosphors were well matched with excitation and emission wavelengths of phytochrome P_R. Therefore, from the entire investigation and obtained results it was concluded that the synthesized Ca_0.995Mg₂(SO₄)₃:0.5mol%Eu²⁺ phosphor has huge potential for plant cultivation application.     

Synthesis and luminescence of Eu3+‐doped in triple phosphate Ca8MgBi(PO4)7 with whitlockite structure

Triple whitlockite‐type structure‐based red phosphors Ca₈MgBi_1?x(PO₄)₇:xEu³⁺ (x = 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80 and 1.00) were synthesized by a conventional solid‐state reaction route and characterized by their X‐ray crystal structures. The X‐ray diffraction (XRD) patterns, Fourier transform infrared spectra, morphologies, photoluminescence spectra, UV/Vis reflectance spectra, decay times and the International Commission on Illumination (CIE) chromaticity coordinates of Ca₈MgBi_1?x(PO₄)₇:xEu³⁺ were analyzed. Eu‐doped Ca₈MgBi(PO₄)₇ phosphors exhibited strong red luminescence with peaks at 616 nm due to the ⁵D₀ → ⁷ F₂ electric dipole transition of Eu³⁺ ions after excitation at 396 nm. The UV/Vis spectra indicated that the band gap of Ca₈MgBi_0.30(PO₄)₇:0.70Eu³⁺ is larger than that of Ca₈MgBi(PO₄)₇. The phosphor developed in this study has great potential as a red‐light‐emitting phosphor for UV light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Photoluminescent properties of Eu3+‐Eu2+ activated MAl2SixO2x + 4 (M = Mg,Ca, Sr,Ba) phosphors prepared in air

In this paper, MAl₂Si_xO_2x+4:Eu²⁺/Eu³⁺ (Eu²⁺ + Eu³⁺ = 2%, molar ratio; M = Mg, Ca, Sr, Ba; x = 0, 0.5, 1, 1.5, 2) phosphors with different SiO₂ concentrations (the ratio of SiO₂ to MAl₂O₄ is n%, n = 0, 50, 100, 150, 200, respectively) were prepared by high‐temperature solid‐state reaction under atmospheric air conditions. Their structures and photoluminescent properties were systematically researched. The results indicate that Eu³⁺ ions have been reduced and Eu²⁺ ions are obtained in air through the self‐reduction mechanism. The alkaline earth metal ions and doping SiO₂ strongly affect the crystalline phase and photoluminescent properties of samples, including microstructures, relative intensity of Eu²⁺ to Eu³⁺, location of emission lines/bands. It is interesting and important that the emission color and intensities of europium‐doped various phosphors which consist of aluminosilicate matrices prepared under atmospheric air conditions could be modulated by changing the kinds of alkaline earth metal and the content of SiO₂.     

Photoluminescence properties of LiTi2 − xEux(PO4)3 phosphor

A solid‐state reaction route‐based LiTi_{2 ? x}Eu_x(PO₄)₃ was phosphor synthesized for the first time to evaluate its luminescence performance by excitation, emission and lifetime (τ) measurements. The LiTi_{2 ? x}Eu_x(PO₄)₃ phosphor was excited at λ_exci. = 397 nm to give an intense orange–red (597 nm) emission attributed to the ⁵D₀ → ⁷F₁ magnetic dipole (ΔJ = ±1) transition and red (616 nm) emission (⁵D₀ → ⁷F₂), which is an electric dipole (ΔJ = ±2) transition of the Eu³⁺ ion. Beside this, excitation and emission spectra of host LiTi₂(PO₄)₃ powder were also reported. The effect of Eu³⁺ concentration on luminescence characteristics was explained from emission and lifetime profiles. Concentration quenching in the LiTi_{2 ? x}Eu_x(PO₄)₃ phosphor was studied from the Dexter's model. Dipole–quadrupole interaction is found to be responsible for energy transfer among Eu³⁺ ions in the host lattice. The LiTi_{2 ? x}Eu_x(PO₄)₃ phosphor displayed a reddish‐orange colour realized from a CIE chromaticity diagram. We therefore suggest that this new phosphor could be used as an optical material of technological importance in the field of display devices. Copyright © 2016 John Wiley & Sons, Ltd.     

Solid‐state synthesis and luminescent properties of yellow‐emitting phosphor NaY(MoO4)2:Dy3+ for white light‐emitting diodes

A yellow‐emitting phosphor NaY(MoO₄)₂:Dy³⁺ was synthesized using a solid‐state reaction at 550 °C for 4 h, and its luminescent properties were investigated. Its phase formation was studied using X‐ray powder diffraction analysis, and there were no crystalline phases other than NaY(MoO₄)₂. NaY(MoO₄)₂:Dy³⁺ produced yellow emission under 386 or 453 nm excitation, and the prominent luminescence was yellow (575 nm) due to the ⁴ F_9/2→⁶H_13/2 transition of Dy³⁺. For the 575 nm emission, the excitation spectrum had one broad band and some narrow peaks; the peaks were located at 290, 351, 365, 386, 426, 453 and 474 nm. Emission intensities were influenced by the Dy³⁺ doping content and a concentration quenching effect was observed; the phenomenon was also proved by the decay curves. Moreover, the Commission International de I'Eclairage chromaticity coordinates of NaY(MoO₄)₂:Dy³⁺ showed similar values at different Dy³⁺ concentrations, and were located in the yellow region. Copyright © 2015 John Wiley & Sons, Ltd.     

Photoluminescence and electron paramagnetic resonance properties of a potential phototherapic agent: MMgF4:Gd3+ (M = Ba,Sr) sub‐microphosphors

Novel narrow band UVB‐emitting phosphors, BaMgF₄:Gd³⁺ and SrMgF₄:Gd³⁺ phosphors, were synthesized using a co‐precipitation synthesis method. X‐Ray diffraction analysis was carried out to confirm compound formation, phase purity and crystallinity of the phosphor. At 274 nm excitation, phosphors show a sharp narrow band emission at 313 nm that can be assigned to ⁶P_7/2 → ⁸S_7/2 transition of the Gd³⁺ ion. With increasing dopant concentration, intensity enhances and then decreases after a certain concentration, which is an indication of concentration quenching taking place in the phosphor. Scanning electron microscopy images of the phosphor show agglomerated particles in the sub‐micron range. Particles range in size from 600 to 800 nm. Electron paramagnetic resonance studies of the phosphors were carried out to detect radicals present in the prepared phosphor. With narrow band UVB emission, phosphor seems to be a good candidate for UV phototherapy application. Copyright © 2016 John Wiley & Sons, Ltd.     

Sol–gel synthesis and luminescence property of Sr4Al2O7:Re3+,R+ (Re = Eu and Dy; R = Li,Na and K) phosphors for white LEDs

Sr₄Al₂O₇:Eu³⁺ and Sr₄Al₂O₇:Dy³⁺ phosphors with alkali metal substitution were prepared using a sol–gel method. The effects of a charge compensator R on the structure and luminescence of Sr₄Al₂O₇:Re³⁺,R⁺ (Re = Eu and Dy; R = Li, Na and K) phosphors were investigated in detail. Upon heating to 1400°C, the structure of the prepared samples was that of the standard phase of Sr₄Al₂O₇. Under ultraviolet excitation, all Sr₄Al₂O₇:Eu³⁺,R⁺ samples exhibited several narrow emission peaks ranging from 550 to 700 nm due to the 4f → 4f transition of Eu³⁺ ions. All Sr₄Al₂O₇:Dy³⁺,R⁺ phosphors showed two emission peaks at 492 and 582 nm, due to the ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions, respectively. The luminescence intensity of Sr₄Al₂O₇:Re³⁺,R⁺ (Re = Eu and Dy; R = Li, Na and K) phosphors improved markedly upon the addition of charge compensators, promoting their application in white light‐emitting diodes with a near‐ultraviolet chip.     

The luminescent properties and crystal structure of Sr(1.5‐x)‐(1.5y)Mg0.5SiO4:xEu2+,yCe3+ blue phosphor synthesized by co‐precipitation method

In order to improve the luminescent performance of silicate blue phosphors, Sr_{(1.5‐x)‐(1.5y)}Mg_0.5SiO₄:xEu²⁺,yCe³⁺ phosphors were synthesized using one‐step calcination of a precursor prepared by chemical co‐precipitation. The crystal structure and luminescent properties of the phosphors were analyzed using X‐ray diffraction and fluorescence spectrophotometry, respectively. Because the activated ions (Eu²⁺) can occupy two different types of sites (Sr₁ and Sr₂), the emission spectrum of Eu²⁺ excited at 350 nm contains two single bands (EM₁ and EM₂) in the wavelength range 400–550 nm, centered at 463 nm, and the emission intensity first increases and then decreases with increasing concentrations of Eu²⁺ ions. Co‐doping of Ce³⁺ ions can greatly enhance the emission intensity of Eu²⁺ by transferring its excitation energy to Eu²⁺. Because of concentration quenching, a higher substitution concentration of Ce³⁺ can lead to a decrease in the intensity. Meanwhile, the quantum efficiency of the phosphor is improved after doping with Ce³⁺, and a blue shift phenomenon is observed in the CIE chromaticity diagram. The results indicate that Sr_{(1.5‐x)‐(1.5y)}Mg_0.5SiO₄:xEu²⁺,yCe³⁺ can be used as a potential new blue phosphor for white light‐emitting diodes.     

Determination of oxytetracycline hydrochloride in milk and egg white samples using Ru(bipy)32+–Ce(SO4)2 chemiluminescence

A novel, rapid and sensitive chemiluminescence (CL) method for the determination of oxytetracycline hydrochloride (OTCH) is described in this paper. The presented method was based on the fact that OTCH could immensely enhance the CL of the reaction of cerium sulfate and tris(2,2‐bipyridyl) ruthenium (II) in acidic medium. Under optimal experimental conditions, CL intensity was favorably linear for OTCH in the range 5.0 × 10^?7 to 5.0 × 10^?5 g/ml, with a detection limit of 1.5 × 10^?7 g/ml (S/N = 3). The relative standard detection was 4.76% for 5.0 × 10^?6 g/ml (n = 11). This method was successfully applied to the analysis of OTCH in milk and egg white samples. According to the results of the kinetic curves for OTCH in the Ru(bipy)₃²⁺–Ce(SO₄)₂ CL system, together with CL and ultraviolet (UV)–visible spectra, the possible mechanism of the CL reaction is discussed briefly.     

Effect of different temperatures to remove reduction gas on the photoluminescence properties of Eu‐doped Li2(Ba1‐xSrx)SiO4 phosphors

In this study, Eu‐doped Li₂(Ba_1‐xSr_x)SiO₄ powders (x = 0, 0.2, 0.4, and 0.6) were synthesized at 850°C in a reduction atmosphere (5% H₂ + 95% N₂) for a duration of 1 h using a solid‐state reaction method. The reduction atmosphere was infused as the synthesis temperature reached 850°C, and was removed as the temperature dropped to 800–500°C. Li₂(Ba_1‐xSr_x)SiO₄ (or Li₂BaSiO₄), (Ba,Sr)₂SiO₄ (or BaSiO₄), and Li₄SiO₄ phases co‐existed in the synthesized Eu‐doped Li₂(Ba_1‐xSr_x)SiO₄ powders. A new finding was that the reduction atmosphere removing (RAR) temperature of the Li₂(Ba_1‐xSr_x)SiO₄ phosphors had a large effect on their photoluminescence excitation (PLE) and PL properties. Except for the 800°C‐RAR‐treated Li₂BaSiO₄ phosphor, PLE spectra of all other Li₂(Ba_1‐xSr_x)SiO₄ phosphors had one broad emission band with two emission peaks centred at ~242 and ~283 nm; these PL spectra had one broad emission band with one emission peak centred at 502–514 nm. We showed that the 800°C‐RAR‐treated Li₂BaSiO₄ phosphor emitted a red light and all other Li₂(Ba_1‐xSr_x)SiO₄ phosphors emitted a green light. Reasons for these results are discussed thoroughly.