Tunable white light emission from single‐phased Li2SrSiO4:Dy3+ phosphors by co‐doping with Eu3+

A series of single‐phase full‐color emitting Li₂Sr_1−x−ySiO₄:xDy³⁺,yEu³⁺ phosphors were synthesized by solid‐state reaction and characterized by X‐ray diffraction and photoluminescence analyses. The samples showed emission peaks at 488 nm (blue), 572 nm (yellow), 592 nm (orange) and 617 nm (red) under 393 nm excitation. The photoluminescence excitation spectra, comprising the Eu–O charge transfer band and 4f–4f transition bands of Dy³⁺ and Eu³⁺, range from 200 to 500 nm. The Commission Internationale de I'Eclairage chromaticity coordinates for Li₂Sr_0.98−xSiO₄:0.02Dy³⁺,xEu³⁺ phosphors were simulated. By manipulating Eu³⁺ and Dy³⁺ concentrations, the color points of Li₂Sr_1−x−ySiO₄:xDy³⁺,yEu³⁺ were tuned from the greenish‐white region to white light and eventually to reddish‐white region, demonstrating that a tunable white light can be obtained by Li₂Sr_1−x−ySiO₄:xDy³⁺,yEu³⁺ phosphors. Li₂Sr_0.98−xSiO₄:0.02Dy³⁺, xEu³⁺ can serve as a white‐light‐emitting phosphor for phosphor‐converted light‐emitting diode. Copyright © 2014 John Wiley & Sons, Ltd.     

Eu3+‐activated Y2MoO6: a narrow band red‐emitting phosphor with strong near‐UV absorption

Near‐UV excited narrow line red‐emitting phosphors, Eu³⁺‐activated Y₂MoO₆ systems, were synthesized using a simple molten salt reaction. The structure and photoluminescence characteristics were investigated using X‐ray powder diffraction, UV–Vis absorption and fluorescent spectrophotometry. The excitation spectra show strong broad‐band absorptions in the near‐UV to blue light regions which match the radiation of near‐UV light‐emitting diode chips well. Under excitation of either near‐UV or blue light, intense red emission with a main peak of 611 nm is observed, ascribed to the ⁵D₀–⁷F₂ transition of Eu³⁺ ions; the optimal doping concentration is 20 mol%. The chromaticity coordinates (x = 0.65, y = 0.34) of the as‐obtained phosphor are very close to the National Television Standard Committee standard values (x = 0.67, y = 0.33). All these characteristics suggest that this material is a promising red‐emitting phosphor candidate for white‐LEDs based on near‐UV LED chips. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

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.     

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 behavior of Li2Sr1‐3x/2EuxSiO4 red phosphors for LED applications

Red‐emitting Li₂Sr_1‐3x/2Eu_xSiO₄ 0≤x≤0.5) phosphors were synthesized at 900°C in air by a solid‐state reaction. The synthesized phosphors were characterized by X‐ray powder diffraction, photoluminescence (PL) excitation (PLE) and PL spectra. The results from the PLE spectra suggest that the strong 394 nm excitation peak associated with the ⁵L₆ state of Eu³⁺ ions is of significance for near ultraviolet pumped white light‐emitting diodes and solid‐state lighting. It is also noted that the position of the charge transfer state of Eu³⁺ ions shifts towards the higher energy side (blue shift) by increasing the content of Eu³⁺ ions. The predominant emissions of Eu³⁺ ions under 394 nm excitation are observed at 580, 593, 614, 656 and 708 nm, which are attributed to the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3 and 4), respectively. The PL results reveal that the optimal content of the red‐emitting Li₂Sr_1‐3x/2Eu_xSiO₄ phosphors is x = 0.475. Simulation of the white light excited by 394 nm near ultraviolet light has also been carried out for its potential white light‐emitting diode applications. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

Luminescent properties of single‐phase Ba2‐x‐1.5y‐1.5zP2O7:xEu2+,yCe3+, zTb3+ phosphors for white light‐emitting diode

A series of Ba₂P₂O₇:xEu²⁺,yCe³⁺,zTb³⁺ phosphors was synthesized via a co‐precipitation method, then their crystal structure, quantum efficiency and luminescent properties were analyzed by XRD and FL, respectively. The results showed that these phosphors not only presented the excitation characteristics of Ba₂P₂O₇:xEu²⁺,zTb³⁺, but also exhibited that of the Ba₂P₂O₇:yCe³⁺,zTb³⁺ phosphor. Meanwhile, the tri‐doped phosphor showed a stronger absorption around 320 nm in contrast with the Eu²⁺/Ce³⁺:Tb³⁺ co‐doped phosphor. Not only can energy transfer from Ce³⁺→Eu²⁺ be observed; the energy transfer mechanism from Eu²⁺ to Tb³⁺ is discussed in the tri‐doped system. Ce³⁺ affects the luminescence properties of Ba₂P₂O₇:xEu²⁺,yCe³⁺,zTb³⁺ phosphors just as the sensitizer whereas Eu²⁺ is considered both as the sensitizer and the activator. The chromaticity coordinates of tri‐doped phosphors excited at 320 nm stayed steadily in the bluish‐white light region,and the emitted color and color temperature (CCT) of these phosphors could be tuned by adjusting the relative contents of Eu²⁺, Ce³⁺ and Tb³⁺. Hence, the single phase Ba₂P₂O₇:xEu²⁺,yCe³⁺,zTb³⁺ phosphors may be considered as potential candidates for white light‐emitting diodes.     

ZnWO4:Eu3+ phosphor with intense blue LED excitation: photoluminescence and electron density distribution analysis

A high intensity 464 nm excitable ZnWO₄:Eu³⁺ red‐emitting phosphor for warm white lighting applications was prepared using a solid‐state reaction method by varying the dopant Eu³⁺ concentration. Crystalline purity and phase identification was confirmed and revealed using powder X‐ray diffraction and Rietveld refinement analysis. The surface morphology of Zn_1‐xEu_xWO₄ (x = 0, 0.01, 0.02, 0.03, 0.04 and 0.05) was examined using scanning electron microscopy (SEM) techniques. From SEM analysis, the ZnWO₄:Eu³⁺ phosphor prepared at 1–3% molar Eu³⁺ concentrations exhibited a small pebble‐like morphology with a smooth surface. On increasing the molar concentration of Eu³⁺ to >3%, the pebble stone morphology disappeared and a large, smooth irregular polygon‐shaped granular‐like morphology was obtained. Of the higher mol% Eu³⁺, the 4% Eu³⁺‐doped ZnWO₄ showed the best photoluminescence properties with high intensity and sharp excitation at 395 and 464 nm, followed by red emission centred at 615 nm with excellent CIE coordinates (x = 0.58 and y = 0.41) in the core red region. Elemental composition and chemical state analysis were carried out for the 4% Eu³⁺‐doped ZnWO₄ phosphor using X‐ray photoelectron spectroscopy and energy dispersive X‐ray spectroscopy studies. Based on all the above analyses, the Eu³⁺‐doped ZnWO₄ phosphor was found to be a very efficient red‐emitting phosphor under near‐UV light as well as under visible light excitation and could be used for white LED and field emissive displays applications.     

Tunable luminescence and energy transfer in Ca3SiO4Cl2:Ce3+,Li+,Mn2+,Eu2+ phosphors

A series of color‐tunable Ca_{3–2x‐y‐z}SiO₄Cl₂ (CSC):xCe³⁺,xLi⁺,yMn²⁺,zEu²⁺ phosphors with low temperature phase structure was synthesized via the sol–gel method. An energy transfer process from Ce³⁺ to Mn²⁺ in CSC:0.01Ce³⁺,0.01Li⁺,yMn²⁺ (y = 0.03–0.09) and the mechanism was verified to be an electric dipole–dipole interaction. The Ce³⁺ and Mn²⁺ emission intensities were greatly enhanced by co‐doping Eu²⁺ ions into CSC:0.01Ce³⁺,0.01Li⁺,0.07Mn²⁺ phosphors due to competitive energy transfers from Eu²⁺/Ce³⁺ to Mn²⁺, and Ce³⁺ to Eu²⁺. Under 332 nm excitation, CSC:0.01Ce³⁺,0.01Li+,0.07Mn²⁺,zEu²⁺ (z = 0.0005–0.002) exhibited tunable emission colors from green to white with coexisting orange, green and violet‐blue emissions. These phosphors could have potential application in white light‐emitting diodes.     

Luminescence study of Eu3+doped Li6Y(BO3)3 phosphor for solid‐state lighting

In this study, Li₆Y_1–xEu_x(BO₃)₃ phosphor was successfully synthesized using a modified solid‐state diffusion method. The Eu³⁺ ion concentration was varied at 0.05, 0.1, 0.2, 0.5 and 1 mol%. The phosphor was characterized for phase purity, morphology, luminescent properties and molecular transmission at room temperature. The XRD pattern suggests a result closely matching the standard JCPDS file (#80‐0843). The emission and excitation spectra were followed to discover the luminescence traits. The excitation spectra indicate that the current phosphor can be efficiently excited at 395 nm and at 466 nm (blue light) to give emission at 595 and 614 nm due to the ⁵D₀ → ⁷F_j transition of Eu³⁺ ions. Concentration quenching was observed at 0.5 mol% Eu³⁺ in the Li₆Y_1–xEu_x(BO₃)₃ host lattice. Strong red emission with CIE chromaticity coordinates of phosphor is x = 0.63 and y = 0.36 achieved with dominant red emission at 614 nm the ⁵D₀ → ⁷ F₂ electric dipole transition of Eu³⁺ ions. The novel Li₆Y_1–xEu_x(BO₃)₃ phosphor may be a suitable red‐emitting component for solid‐state lighting using double‐excited wavelengths, i.e. near‐UV at 395 nm and blue light at 466 nm. 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.     

A novel red‐emitting phosphor,KAl1‐xPO4Cl:Eux3+ (0.1 ≤ x ≤ 1.0)

A series of phosphors KAl_1‐xPO₄Cl:Eu_x³⁺ (0.1 ≤ x ≤ 1.0) was synthesized using a facile combustion method using urea as a fuel and their structural, morphological and photoluminescence properties were investigated. It was found that the particle size was in the range of 1–2 µm with an irregular shape. The f–f transitions of Eu³⁺ in the host lattice were assigned and discussed. The excitation and emission spectra indicated that this phosphor can be efficiently excited by ultraviolet (395 nm), and exhibit reddish orange emission corresponding to the ⁵D₀→⁷F_J (J = 0, 1, 2) transitions of Eu³⁺. The impact of the Eu³⁺ concentration on the relative emission intensity was investigated, and the best doping concentration is 0.5. The present study suggests that the KAl_0.5PO₄Cl: Eu_0.5³⁺ phosphor is a strong candidate as a red component for phosphor‐ converted white light‐emitting diodes (LEDs). Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

Optical characterization and the energy level scheme for Ce3+‐doped BaY2Si3O10 blue‐emitting phosphor

A series of Ce³⁺‐activated blue‐emitting phosphors BaY₂Si₃O₁₀ (BYSO) was designed and synthesized by a conventional solid‐state method. Upon ultraviolet light (250–370 nm) excitation, the obtained phosphors showed an intense blue emission band centered at 400–427 nm depending on doping concentration, and corresponding to the 5d→4f transition of Ce³⁺. The effects of doping concentration on crystal structure, emitting color, photoluminescence and photoluminescence excitation spectra, as well as the concentration quenching mechanism were studied in detail. The optimal doping concentration of Ce³⁺ in this phosphor was demonstrated to be about 0.75% and the concentration quenching mechanism can be ascribed to electric dipole–dipole interactions with a critical distance of ~38 Å. These fine luminescence properties indicate that BYSO:Ce³⁺ may be a potential blue phosphor for full‐color ultra‐violet (UV) white light emitting diodes (WLEDs).     

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.     

Luminescent properties of MAl(SO4)2Br:Eu3+ (M = Sr or Mg) red phosphors for near‐UV light‐emitting diodes

Eu³⁺‐activated MAl(SO₄)₂Br phosphors (where M = Mg or Sr) are successfully prepared using a wet chemical reaction technique. The samples are characterized by X‐ray diffraction (XRD) and photoluminescence (PL) spectroscopies. The XRD pattern revealed that both the samples are microcrystalline in nature. PL of Eu³⁺‐doped SrAl(SO₄)₂Br and MgAl(SO₄)₂Br phosphors exhibited characteristic red emission coming from the ⁵D₀ → ⁷F₂ (616 nm) electron transition, when excited by 396 nm wavelength of light. The maximum intensity of luminescence was observed at a concentration of 1 mol% Eu³⁺. The intensity of the electric dipole transition at 616 nm is greater than that of the magnetic dipole transition at 594 nm. The results showed that MAl(SO₄)₂Br:Eu³⁺, (M = Mg, Sr) phosphors have potential application in near‐UV light‐emitting diodes as efficient red‐emitting phosphor. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and photoluminescence of EuII in barium zinc orthosilicate: a novel green color emitting phosphor for white‐LEDs

A series of Eu²⁺‐activated barium orthosilicates (BaZnSiO₄) were synthesized using a high‐temperature solid‐state reaction. A photoluminescence excitation study of Eu²⁺ shows a broad absorption band in the range of 270–450 nm, with multiple absorption peak maxima (310, 350 and 400 nm) due to 4f–5d electronic transition. The emission spectra of all the compositions show green color emission (in the spectral region 450–550 nm with a peak maximum at 502 nm and a shoulder at ~ 490 nm) with appropriate Comission Internationale de l'Eclairage (CIE) color coordinates. The two emission peaks are due to the presence of Eu²⁺ in two different Ba sites in the BaZnSiO₄ host lattice. The energy transfers between the Eu²⁺ ions in BaZnSiO₄ host are elucidated from the critical concentration quenching data based on the electronic multipolar interaction. All Eu²⁺‐activated BaZnSiO₄ phosphor materials can be efficiently excited in the ultraviolet (UV) to near UV‐region (270–420 nm), making them attractive candidate as a green phosphor for solid state lighting–white light‐emitting diodes.     

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.     

Intense green‐, red‐emitting Tb3+, Tb3+/Bi3+‐doped and Sm3+, Sm3+/La3+‐doped Ca2Al2SiO7 phosphors

This paper focuses on an optical study of a Tb³⁺/Bi³⁺‐doped and Sm³⁺/La³⁺‐ doped Ca₂Al₂SiO₇ phosphor synthesized using combustion methods. Here, Ca₂Al₂SiO₇:Sm³⁺ showed a red emission band under visible light excitation but, when it co‐doped with La³⁺ ions, the emission intensity was further enhanced. Ca₂Al₂SiO₇:Tb³⁺ shows the characteristic green emission band under near‐ultraviolet light excitation wavelengths, co‐doping with Bi³⁺ ions produced enhanced photoluminescence intensity with better colour tunable properties. The phosphor exhibited better phase purity and crystallinity, confirmed by X‐ray diffraction. Binding energies of Ca(2p), Al(2p), Si(2p), O(1s) were studied using X‐ray photoelectron spectroscopy. The reported phosphor may be a promising visible light excited red phosphor for light‐emitting diodes and energy conversion devices.