The luminescence properties of Sr2–1.5x−1.5yP2O7:xDy3+,yCe3+ phosphor for near‐UV‐based white LEDs synthesized by a chemical co‐precipitation method

A series of Sr₂P₂O₇:Dy³⁺, Sr₂P₂O₇:Ce³⁺ and Sr₂P₂O₇:Dy³⁺,Ce³⁺ phosphors was synthesized via the one‐step calcination process for the precursors prepared by co‐precipitation methods. The phases, morphology, quantum efficiency and photoluminescence properties of the obtained phosphors were characterized systematically. These results show that the near‐spherical particles prepared through calcining the precursors by means of ammonium dibasic phosphate co‐precipitation (method 3) have the smallest particle size and strongest emission intensity among the three methods in the paper. With Dy³⁺ concentration increasing in Sr₂P₂O₇:Dy³⁺ phosphors, the luminescence intensity first increases, reaches maximum, and then decreases. A similar trend was followed by Sr₂P₂O₇:Ce³⁺ with Ce³⁺concentration increasing. A successful attempt was made to initiate the energy transfer mechanism from Ce³⁺ to Dy³⁺ in the host lattice and an overlap between the emission band of Ce³⁺ and the excitation band of Dy³⁺ indicated that the Ce³⁺ → Dy³⁺ energy transfer may indeed exist. It is clear that the photoluminescence intensity of Dy³⁺ as well as the quantum efficiency of the phosphor can be enhanced markedly by co‐doping Ce³⁺. Sr₂P₂O₇:Dy³⁺,Ce³⁺ has its (CIE) chromaticity coordinates in the bluish‐white‐light region, near the standard illuminant D₆₅. The CIE 1913 chromaticity coordinates of Sr₂P₂O₇:Dy³⁺ phosphors fall in the white‐light region, and are adjacent to the ideal white‐light coordinates. In addition, the colour temperature and colour tone of Sr₂P₂O₇:Dy³⁺ could be adjusted by changing the relative concentration of Dy³⁺. In short, Sr₂P₂O₇:Dy³⁺ can be a promising single‐phased white‐light emitting phosphor for near‐UV (NUV) w‐LEDs.     

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.     

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.     

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.     

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.     

Structural characterization of Er3+,Yb3+‐doped Gd2O3 phosphor,synthesized using the solid‐state reaction method,and its luminescence behavior

We report the synthesis and structural characterization of Er³⁺,Yb³⁺‐doped Gd₂O₃ phosphor. The sample was prepared using the conventional solid‐state reaction method, which is the most suitable method for large‐scale production. The prepared phosphor sample was characterized using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermoluminescence (TL), photoluminescence (PL) and CIE techniques. For PL studies, the excitation and emission spectra of Gd₂O₃ phosphor doped with Er³⁺ and Yb³⁺ were recorded. The excitation spectrum was recorded at a wavelength of 551 nm and showed an intense peak at 276 nm. The emission spectrum was recorded at 276 nm excitation and showed peaks in all blue, green and red regions, which indicate that the prepared phosphor may act as a single host for white light‐emitting diode (WLED) applications, as verified by International de I'Eclairage (CIE) techniques. From the XRD data, the calculated average crystallite size of Er³⁺ and Yb³⁺‐doped Gd₂O₃ phosphor is ~ 38 nm. A TL study was carried out for the phosphor using UV irradiation. The TL glow curve was recorded for UV, beta and gamma irradiations, and the kinetic parameters were also calculated. In addition, the trap parameters of the prepared phosphor were also studied using computerized glow curve deconvolution (CGCD). Copyright © 2015 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.     

Luminescence and energy‐transfer properties of color‐tunable Ca2Mg0.25Al1.5Si1.25O7:Ce3+/Eu2+/Tb3+ phosphors for ultraviolet light‐emitting diodes

A series of Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺/Eu²⁺/Tb³⁺ phosphors was been prepared via a conventional high temperature solid‐state reaction and their luminescence properties were studied. The emission spectra of Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Eu²⁺ and Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Tb³⁺ phosphors show not only a band due to Ce³⁺ ions (409 nm) but also as a band due to Eu²⁺ (520 nm) and Tb³⁺ (542 nm) ions. More importantly, the effective energy transfer from Ce³⁺ to Eu²⁺ and Tb³⁺ ions was confirmed and investigated by emission/excitation spectra and luminescent decay behaviors. Furthermore, the energy level scheme and energy transfer mechanism were investigated and were demonstrated to be of resonant type via dipole–dipole (Ce³⁺ to Eu²⁺) and dipole–quadrupole (Ce³⁺ to Tb³⁺) reactions, respectively. Under excitation at 350 nm, the emitting color could be changed from blue to green by adjusting the relative doping concentration of Ce³⁺ and Eu²⁺ ions as well as Ce³⁺ and Tb³⁺ ions. The above results indicate that Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Eu²⁺/Tb³⁺ are promising single‐phase blue‐to‐green phosphors for application in phosphor conversion white‐light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

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.     

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.     

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.     

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.     

Determination of nucleic acid by [tetra‐(3‐methoxy‐4‐hydroxyphenyl)]–Tb3+ porphyrin as the fluorescence spectral probe in bis(2‐ethylhexyl)sulfosuccinate sodium salt micelle system

A new system for the determination of nucleic acid by rare earth metallic porphyrin of [tetra‐(3‐methoxy‐4‐hydroxyphenyl)]–Tb³⁺ [T(3‐MO‐4HP)–Tb³⁺] porphyrin as fluorescence spectral probe has been developed in this paper. Nucleic acid can enhance the fluorescence intensity of the T(3‐MO‐4HP)–Tb³⁺ porphyrin in the presence of bis(2‐ethylhexyl)sulfosuccinate sodium salt(AOT) micelle. In pH 8.00 Tris–HCl buffer solution, under optimum conditions, the enhanced fluorescence intensity is in proportion to the concentration of nucleic acids in the range of 0.05–3.00 µg mL^?1 for calf thymus DNA (ct DNA) and 0.03–4.80 µg mL^?1 for fish sperm DNA(fs DNA). Their detection limits are 0.03 and 0.01 µg mL^?1, respectively. In addition, the binding interaction mechanism between T(3‐MO‐4HP)–Tb³⁺ porphyrin and ct DNA is also investigated by resonance scattering and fluorescence spectra. The maximum binding number is calculated by molar ratio method. The new system can be used for the determination of nucleic acid in pig liver, yielding satisfactory results. Copyright © 2009 John Wiley & Sons, Ltd.