The effects of charge compensation on photoluminescence properties of a new green‐emitting ZnB2O4:Tb3+ phosphor

Charge compensation is an effective way to eliminate charge defects and improve the luminescent intensity of phosphors. In this paper, a new green‐emitting phosphor ZnB₂O₄:Tb³⁺ was prepared by solid‐state reaction at 750°C. The effects of Tb³⁺ doping content and charge compensators (Li⁺, Na⁺ or K⁺) on photoluminescence properties of ZnB₂O₄:Tb³⁺ were investigated. X‐ray powder diffraction analysis confirms the sample has cubic structure of ZnB₂O₄. The excitation and emission spectra indicate that this phosphor can be excited by near ultraviolet light at 378 nm, and exhibits bright green emission with the highest peak at 544 nm corresponding to the ⁵D₄→⁷F₅ transition of Tb³⁺. The critical quenching concentration of Tb³⁺ in ZnB₂O₄ host is 8 mol%. The results of charge compensation show that the emission intensity can be improved by Na⁺ and K⁺. Specifically, K⁺ is the optimal one for ZnB₂O₄:Tb³⁺. Copyright © 2014 John Wiley & Sons, Ltd.     

Luminescent properties and energy transfer in the green phosphors LaBSiO5:Tb3+,Ce3+

LaBSiO₅ phosphors doped with Ce³⁺ and Tb³⁺ were synthesized using the conventional solid‐state method at 1100 °C. The phase purity and luminescent properties of these phosphors are investigated. LaBSiO₅:Tb³⁺ phosphors show intense green emission, and LaBSiO₅ phosphors doped with Ce³⁺ show blue–violet emission under UV light excitation. LaBSiO₅ phosphors co‐doped with Ce³⁺ and Tb³⁺ exhibit blue–violet and green emission under excitation by UV light. The blue–violet emission is due to the 5d–4f transition of Ce³⁺ and the green emission is ascribed to the ⁵D₄ → ⁷ F₅ transition of Tb³⁺. The spectral overlap between the excitation band of Tb³⁺ and the emission band of Ce³⁺ supports the occurrence of energy transfer from Ce³⁺ to Tb³⁺, and the energy transfer process was investigated. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

White light emission and energy transfer of LaMgAl11O19:Eu3+, Tb3+ phosphors

White-light-tunable LaMgAl₁₁O₁₉:x%Tb³⁺, y%Eu³⁺ series phosphors were prepared using the gel-combustion method. The structure and luminescence properties were studied, and the energy transfer of Eu³⁺ and Tb³⁺ in the LaMgAl₁₁O₁₉ system was also discussed. The results showed that the LaMgAl₁₁O₁₉ matrix exhibited strong emission in the blue-light region under the excitation of ultraviolet light, which resulted in conditions suitable for the preparation of white-light-tunable phosphors. The emission spectra of LaMgAl₁₁O₁₉:2%Tb³⁺, y%Eu³⁺ (y = 2%–9%) series phosphors were obtained through optimization experiments. It could be seen from the CIE diagram that by adjusting the doping quantities of Eu³⁺ and Tb³⁺ in the LaMgAl₁₁O₁₉ host, multicolor luminescence and white light emission in a single host could be achieved. By calculating the energy transfer efficiency and critical distance between Eu³⁺ and Tb³⁺ series phosphors, the mechanism of energy transfer between Tb³⁺ and Eu³⁺ was found to be the interaction between electric quadruples.     

Tunable emission from LiBaBO3:Eu3+;Bi3+ phosphor for solid‐state lighting

Europium (Eu³⁺) and bismuth (Bi³⁺) co‐activated LiBaBO₃ powder phosphors were synthesized by a solid‐state reaction and the structure, particle morphology, optical and photoluminescent properties were investigated. X‐Ray diffraction patterns of the LiBaBO₃ phosphors crystallized in a pure monoclinic phase, i.e. there were no secondary phases due to either incidental impurities or undecomposed starting materials. Scanning electron microscopy images showed that the powders were made up of fluffy needle‐like particles that were randomly aligned. The band‐gap of the LiBaBO₃ host was estimated to be 3.33 eV from the UV/vis absorption data. Blue emission was observed from the LiBaBO₃ host, which is ascribed to self‐activation of the host matrix. In addition, greenish‐blue (493 nm) and red (613 nm) emissions were observed from europium‐doped samples and were attributed to the emissions of Eu²⁺ and Eu³⁺, respectively. Furthermore, after codoping with Bi³⁺, the emission intensity of Eu³⁺ located at 613 nm was significantly enhanced. From the Commission Internationale de I′Eclairage (CIE) color coordinates, white emission was observed from LiBa_1–xBO₃:xEu³⁺ (x = 0.020 and 0.025) phosphor powders with color coordinates of x = 0.368, y = 0.378 and x = 0.376, y = 0.366, respectively.     

Tunable warm white light emission and energy transfer of Dy3+ co-doped Sr2LaZrO5.5:Eu3+ phosphors

Eu³⁺,Dy³⁺ co-doped Sr₂LaZrO_5.5-based phosphors were prepared through a sol–gel method. Through characterization, it was found that the Sr₂LaZrO_5.5-based fluorescent powder co-doped with Eu³⁺ and Dy³⁺ had a cubic structure. At an excitation wavelength of 290 nm, the substrate Sr₂LaZrO_5.5 exhibited strong blue emission at 468 nm, and the Sr₂LaZrO_5.5:18%Eu³⁺ phosphor exhibited a strong red emission peak at 612 nm. When the doping amount of Dy³⁺ was 5, 8, 12, 15, or 18%, the Sr₂LaZrO_5.5:18%Eu³⁺ phosphor changed from an orange-red light, to a warm white light, and to a cold white light. According to the emission spectra, the emission intensities of the substrates Sr₂LaZrO_5.5 and Sr₂LaZrO_5.5:Eu³⁺ decreased with increasing Dy³⁺ concentration, confirming the energy transfer between the host Sr₂LaZrO_5.5-Eu³⁺,Dy³⁺, and resulting in a lower CCT value, with significantly improved white light emission.     

A novel n-UV convertible colour-tunable emitting oxynitride phosphor: Realization based on Ce3+-Tb3+ energy transfer

In the present work, a novel n-UV convertible colour-tunable emitting phosphor was obtained based on the efficient Ce³⁺-Tb³⁺ energy transfer in the Y₁₀Al₂Si₃O₁₈N₄ host. By properly controlling the ratio of Ce³⁺/Tb³⁺, the colour hue of the obtained powder covered the blue and green regions, under excitation of 365 nm. The steady-state and dynamic-state luminescence measurement was performed to shed light on the related mechanism, which was justified by the electronic dipole–quadrupole dominating the related energy transfer process. Preliminary studies showed that Y₁₀Al₂Si₃O₁₈N₄:Ce³⁺,Tb³⁺ can be promising as an inorganic phosphor for white LED applications.     

Tunable luminescence properties and energy transfer in LaAl11O18:Eu,Tb phosphor

Eu²⁺ and Tb³⁺ singly doped and co‐doped LaAl₁₁O₁₈ phosphors were prepared by a combustion method using urea as a fuel. The phase structure and photoluminescence (PL) properties of the prepared phosphors were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence excitation and emission spectra. When the content of Eu²⁺ was fixed at 0.01, the emission chromaticity coordinates could be adjusted from blue to green region by tuning the contents of Tb³⁺ ions from 0.01 to 0.03 through an energy transfer (ET) process. The fluorescence data collected from the samples with different contents of Tb³⁺ into LaAl₁₁O₁₈: Eu, show the enhanced green emission at 545 nm associated with ⁵D₄ –⁷F₅ transitions of Tb³⁺. The enhancement was attributed to ET from Eu²⁺ to Tb³⁺, and therefore Eu²⁺ ion acts as a sensitizer (an energy donor) while Tb³⁺ ion as an activator. The ET from Eu²⁺ to Tb³⁺ is performed through dipole–dipole interaction. The ET efficiency and critical distance were also calculated. The present Eu²⁺–Tb³⁺ co‐doped LaAl₁₁O₁₈ phosphor will have potential application for UV convertible white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Luminescence study of Sm3+,Eu3+-doped Y2Zr2O7 host: optical investigation of greenish yellow to red colour tunable pyrochlore phosphor

Pyrochlore phosphors have shown their worth in modern day lighting in the last few years. Colour tunability of the phosphor is one of the modern techniques used to obtain white light-emitting diodes (WLEDs). In the proposed work, Y₂Zr₂O₇:Sm³⁺,Eu³⁺ phosphors were investigated for WLED applications as well as display devices. A convectional solid-state diffusion method was used to synthesize the proposed phosphors. X-ray diffraction of the proposed phosphors was performed and compared with the standard Inorganic Crystal Structure Database. The crystal structure of the sample was cubic in nature, obtained from Rietveld refinement. Vibrational and morphological studies on the samples were carried out using Fourier transform infrared spectroscopy and scanning electron microscopy analysis. The photoluminescence study of the colour tunable phosphor showed the characteristic peak of Sm³⁺ together with the two sharp peaks of Eu³⁺ ions. Greenish yellow to red colour tunability was observed in the proposed phosphor with enhancement of Eu³⁺ ions. All these results showed the worth of this sample for WLEDs applications as well as in display devices.     

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.     

Influence of rare earth elements (Y,Gd and Lu) on the luminescent properties of green phosphor ZnMoO4:Tb3+

(Zn,Ln_x)MoO₄:Tb³⁺ (Ln = Y³⁺, Gd³⁺ and Lu³⁺) were prepared using the co‐precipitation method. Phase impurity, morphology and composition were investigated by power X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The experimental results show that crystal structure is not destroyed after doping an appropriate amount of Y³⁺, Gd³⁺ and Lu³⁺. EDS analysis reveals that Y, Gd and Lu have been successfully doped into ZnMoO₄. In addition, the morphology of the phosphors is notably improved, exhibiting homogeneous dispersion morphology and irregular shapes of particle size ~ 0.5–1 µm. The luminescent intensity of (Zn,Ln_x)MoO₄:Tb³⁺ (Ln = Y³⁺, Gd³⁺ and Lu³⁺) phosphor is obviously higher than that of ZnMoO₄:Tb³⁺ phosphor. The energy transfer process between trivalent rare earth ions indicates that the inert earth ions can act as an energy bridge from MoO₄^2‐ to Tb³⁺. Copyright © 2013 John Wiley & Sons, Ltd.     

Intensity enhancement of photoluminescence in Tb3+/Eu3+ co-doped Ca14Zn6Al10O35 phosphor for WLEDs

This article focuses on the effect of monovalent cation doping on the optical properties of rare earth (RE = Eu³⁺, Tb³⁺) co-doped Ca₁₄Zn₆Al₁₀O₃₅ which has been synthesized by a low temperature combustion method. Crystalline phase of the Ca₁₄Zn₆Al₁₀O₃₅ phosphor was examined and confirmed by X-ray diffraction measurement. Under near-ultraviolet light excitation Eu³⁺-doped Ca₁₄Zn₆Al₁₀O₃₅ phosphor exhibit characterization of Eu³⁺ emission bands that are located at a maximum wavelength (λ_max) of approximately 470 nm and other peaks centred at 593 nm and 615 nm, respectively. With Tb³⁺-doped Ca₁₄Zn₆Al₁₀O₃₅ phosphor showing a green emission band centred at 544 nm under near-ultraviolet range. Furthermore, we studied the energy transfer process in Eu³⁺/Tb³⁺pair and enhancement in photoluminescence (PL) intensity with doping different charge compensation. Here we obtained the optimum PL emission intensity of the phosphor in broad and intense visible spectral range which may be significant for the fabrication of white light emitting diodes (WLEDs).     

Combustion synthesis and luminescence properties of SrAl2O4:Eu2+, Dy3+, Tb3+ phosphor.

Eu(2+), Dy(3+) and Tb(3+) co-doped strontium aluminate phosphor with high brightness and long afterglow was synthesized by a combustion method, using urea as a reducer. The properties of SrAl(2)O(4):Eu(2+),Dy(3+),Tb(3+) phosphor with a series of initiating combustion temperatures, urea concentrations and boric acid molar fractions were investigated. The sample at initiating combustion temperature of 600 degrees C exhibited an intense emission peak at 513 nm, in which the phosphor existed as a single-phase monoclinic structure. The experimental results showed that the optimum ratio of urea is 2.0 times higher than theoretical quantities and that the suitable molar fraction of H(3)BO(3) is 0.08. The average particle size of the phosphor was 50-80 nm and its luminescence properties were studied systematically. Compared with SrAl(2)O(4):Eu(2+),Dy(3+) phosphor, the initial luminescence brightness improved from 2.50 candela (cd)/m(2) to 3.55 cd/m(2) and the long afterglow time was prolonged from 1290 s to 2743 s.     

Energy transfer process in a rare earth (Ce3+, Dy3+, Sm3+)-doped nanocrystalline phosphate phosphor

This work presents the optimized luminescence spectra for the Ce³⁺,Sm³⁺-doped NaSrPO₄ phosphor that was synthesized using a wet chemical method. Ce³⁺ and Sm³⁺ are activator impurities that show spectral splitting bands that corresponds to the d–f and f–f transitions, respectively. These impurity elements shows the characteristics spectral bands when doped with the NaSrPO₄ host lattice. Spectral splitting in the Ce³⁺ excitation band was monitored in the 240–340 nm range, in which the observed bands were located at 269 nm, 292 nm and 321 nm, and emission bands were observed in the broad spectral range 330–430 nm. However, when Sm³⁺ ion was doped in the same host lattice we obtained a characteristic emission band at 590 and 645 nm in the orange–red region, under sharp excitation bands located at 345, 361, 375, and 403 nm respectively. Also, we carried out energy transfer analysis in the Ce³⁺/Dy³⁺-doped NaSrPO₄ phosphor. Further crystalline phase and the nanophase nature of the phosphor compound were confirmed using X-ray diffraction and transmission electron microscopy analyses.     

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.     

Energy transfer between Ce3+ → Gd3+ or Tb3+ in KNaSO4 microphosphor

KNaSO₄ microphosphor doped with Ce,Gd and Ce,Tb and prepared by a wet chemical method was studied using X‐ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) characterization. KNaSO₄ has a 5‐µm particle size detected by SEM. KNaSO₄:Ce³⁺,Tb³⁺ showed blue and green emission (at 494 nm, 557 nm, 590 nm) of Tb³⁺ due to ⁵D₄ → ⁷F_J (J = 4, 5, 6) transitions. KNaSO₄:Ce³⁺,Gd³⁺ showed luminescence in the ultraviolet (UV) light region at 314 nm for an excitation at 271 nm wavelength. It was observed that efficient energy transfer took place from Ce³⁺ → Gd³⁺ and Ce³⁺ → Tb³⁺ sublattices indicating that Ce³⁺ could effectively sensitize Gd³⁺ or Tb³⁺ (green emission). Ce³⁺ emission weakened and Gd³⁺ or Tb³⁺ enhanced the emission significantly in KNaSO₄. This paper discusses the development and understanding of photoluminescence and the effect of Tb³⁺ and Gd³⁺ on KNaSO₄:Ce³⁺. Copyright © 2015 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.     

Orange light‐emitting Ca3Mg3(PO4)4:Sm3+ phosphors

This work reports the photoluminescence properties of Ca₃Mg₃(PO₄)₄:Sm³⁺ phosphors that were synthesized by the combustion method. The phase formation and morphology of the prepared phosphors were analysed by X‐ray diffraction studies and scanning electron microscopy. Ca₃Mg₃(PO₄)₄:Sm³⁺ phosphors give orange light emission when excited by near‐ultraviolet (NUV) and blue light. The photoluminescence characteristics of the as‐prepared phosphors were investigated and their emission spectra showed three peaks due to ⁴G_5/2 → ⁶H_5/2, ⁴G_5/2 → ⁶H_7/2 and ⁴G_5/2 → ⁶H_9/2 transitions. The mechanism responsible for the concentration quenching of luminescence was found to be an electric dipole–dipole interaction. The CIE chromaticity coordinates suggested that the prepared phosphors are potential candidates for orange light‐emitting diodes (LEDs).     

Intense green light emission and thermoluminescence glow curve analysis of Tb3+-activated CaY2O4 phosphor

Here, the synthesis and luminescence analysis of the Tb³⁺-activated phosphor were reported. The CaY₂O₄ phosphors were synthesized using a modified solid-state reaction method with a variable doping concentration of Tb³⁺ ion (0.1–2.5 mol%). As synthesized, the phosphor was characterized using Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analysis techniques for the optimized concentration of doping ions. The prepared phosphor showed a cubic structure, and FTIR analysis confirmed functional group analysis. It was discovered that the intensity of 1.5 mol% was higher than at other concentrations after the photoluminescence (PL) excitation and emission spectra were recorded for different concentrations of doping ions. The excitation was monitored at 542 nm, and the emission was monitored at 237 nm. At 237 nm excitation, the emission peaks were found at 620 nm (⁵D₄→⁷F₃), 582 nm (⁵D₄→⁷F₄), 542 nm (⁵D₄→⁷F₅), and 484 nm (⁵D₄→⁷F₆). The 1931 CIE (x, y) chromaticity coordinates showed the distribution of the spectral region calculated from the PL emission spectra. The values of (x = 0.34 and y = 0.60) were very close to dark green emission. Therefore, the produced phosphor would be very useful for light-emitting diode (green component) applications. Thermoluminescence glow curve analysis for various concentrations of doping ions and various ultraviolet (UV) exposure times was carried out, and a single broad peak was found at 252°C. The computerized glow curve deconvolution method was used to obtain the related kinetic parameters. The prepared phosphor exhibited an excellent response to UV dose and could be useful for UV ray dosimetry.     

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.