Crystal structure and luminescence properties of the blue‐green‐emitting Ba9(Lu,Y)2Si6O24:Ce3+ phosphor

Samples of the Ba₉(Lu_2‐xY_x)Si₆O₂₄:Ce³⁺ (x = 0–2) blue‐green phosphors were synthesized by solid‐state reactions. All the samples exhibited a rhombohedral crystal structure. As the Y³⁺ concentration increased, the diffraction peaks shifted to the small angle region and the lattice parameters increased due to the larger ionic radius of Y³⁺ (r = 0.900 Å) compared with that of Lu³⁺ (r = 0.861 Å). Under 400 nm excitation, samples exhibited strong blue‐green emissions around 490 nm. The emission bands had a slight blue shift that resulted from weak crystal‐field splitting with increasing Y³⁺ concentration. Luminescence intensity and quantum efficiency (QE) decreased with increasing Y³⁺ concentration. The internal QE decreased from 74 to 50% and the external QE decreased from 50 to 34% as x increased from 0 to 2. The thermal stability of the Lu series was better than that of the Y‐series. The excitation band peak around 400 nm matched well with the emission light from the efficient near‐ultraviolet (NUV) chip. These results indicate promising applications for these NUV‐based white light‐emitting diodes.     

Investigation of UV‐emitting Gd3+‐doped LiCaBO3 phosphor

Incorporating the Gd³⁺ rare earth ion in the LiCaBO₃ host lattice resulted in narrow‐band UV‐B emission peaking at 315 nm, with excitation at 274 nm. The LiCaBO₃:Gd³⁺ phosphor was synthesized via the solid‐state diffusion method. The structural, morphological and luminescence properties of this phosphor were characterized by X‐ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and photoluminescence (PL) spectroscopy. Electron paramagnetic resonance (EPR) characterization of the as‐prepared phosphors is also reported here. XRD studies confirmed the crystal formation and phase purity of the prepared phosphors. A series of different dopant concentrations was synthesized and the concentration‐quenching effect was studied. Critical energy transfer distance between activator ions was determined and the mechanism governing the concentration quenching is also reported in this paper. Copyright © 2015 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).     

Synthesis and luminescence properties of a novel blue emitting phosphor NaMgPO4:Eu2+

A novel blue‐emitting phosphor of Eu²⁺‐activated NaMgPO₄ was prepared by combustion‐assisted synthesis. Sodium dihydrogen phosphate and magnesium nitrate were used as the source of Na, P and Mg, respectively. The ratios of magnesium and phosphorus components that were dissolved into the combustion solution were changed from 1:1 to 1:1.3. Their effect on the crystallinities and photoluminescence spectra of the phosphor particles were investigated. The post‐heated phosphor particles had a broad excitation wavelength that ranged from 240 to 410 nm. The phosphor particles prepared from the combustion solution with a 1:1.2 ratio of magnesium to phosphorus had maximum emission intensity under ultraviolet excitation. The effect of doped Eu²⁺ concentration on the emission intensity of NaMgPO₄:Eu²⁺ was also investigated.     

Effect of Ga3+ and Gd3+ ions substitution on the structural and optical properties of Ce3+‐doped yttrium aluminium garnet phosphor nanopowders

The structural and optical properties of commercially obtained Y₃Al₅O₁₂:Ce³⁺ phosphor were investigated by replacing Al³⁺ with Ga³⁺ and Y³⁺ with Gd³⁺ in the Y₃Al₅O₁₂:Ce³⁺ structure to form Y₃(Al,Ga)₅O₁₂:Ce³⁺ and (Y,Gd)₃Al₅O₁₂:Ce³⁺. X‐Ray diffraction (XRD) results showed slight 2‐theta peak shifts to lower angles when Ga³⁺ was used and to higher angles when Gd³⁺ was used, with respect to peaks from Y₃Al₅O₁₂:Ce³⁺ and JCPDS card no. 73–1370. This could be attributed to induced crystal‐field effects due to the different ionic sizes of Ga³⁺ and Gd³⁺ compared with Al³⁺ and Y³⁺. The photoluminescence (PL) spectra showed broad excitation from 350 to 550 nm with a maximum at 472 nm, and broad emission bands from 500 to 650 nm, centred at 578 nm for Y₃Al₅O₁₂:Ce³⁺ arising from the 5d → 4f transition of Ce³⁺. PL revealed a blue shift for Ga³⁺ substitution and a red shift for Gd³⁺ substitution. UV–Vis showed two absorption peaks at 357 and 457 nm for Y₃Al₅O₁₂:Ce³⁺, with peaks shifting to 432 nm for Ga³⁺ and 460 nm for Gd³⁺ substitutions. Changes in the trap levels or in the depth and number of traps due to Ce³⁺ were analysed using thermoluminescence (TL) spectroscopy. This revealed the existence of shallow and deep traps. It was observed that Ga³⁺ substitution contributes to the shallowest traps at 74 °C and fewer deep traps at 163 °C, followed by Gd³⁺ with shallow traps at 87 °C and deep traps at 146 °C. Copyright © 2016 John Wiley & Sons, Ltd.     

Luminescence of the near‐ultraviolet blue‐emitting Ba9Al2Si6O24:Ce3+ phosphor

A near‐ultraviolet (NUV) blue‐emitting phosphor Ba₉Al₂Si₆O₂₄:Ce³⁺ (BAS:Ce³⁺) was synthesized using a high‐temperature solid‐state reaction. BAS:Ce³⁺ had an excitation band peak at about 328 nm and showed a blue emission band. The NUV‐blue emission band had a peak at about 386 nm with a band width of about 60 nm, attributed to the 5d–4f transition of Ce³⁺. Fluorescent decay showed an exponential model with a lifetime of 27.2 nsec. At 150°C, the luminescence intensity decreased to 68.7% compared with the intensity at room temperature.     

Effect of sintering temperature on the luminescence properties of Ca0.8Ba0.2TiO3:Pr3+ red‐emitting phosphor

Nanoparticles with the nominal composition Ca_0.8Ba_0.2Ti0₃:Pr³⁺ were prepared using the sol–gel process. Barium nitrate, 4‐hydrated calcium nitrate and praseodymium oxide were used as raw materials. The structural evolution and decomposition processes of the precursors were investigated by powder X‐ray diffraction, differential thermal analysis and thermogravimetric analysis. Crystalline Ca_0.8Ba_0.2Ti0₃:Pr³⁺ could be obtained at 700°C. The photoluminescence properties of the samples were investigated using excitation and emission spectra. Ca_0.8Ba_0.2Ti0₃:Pr³⁺ nanoparticles showed strong red emission, which could be assigned to the typical ¹D₂→³H₄ transition of Pr³⁺. Furthermore, the study found that sintering temperature and the introduction of Ba²⁺ influence the decay time of persistent luminescence. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Synthesis and luminescence properties of blue‐emitting phosphor Ca12Al14O32F2:Eu2+ for white light‐emitting diode

A blue‐emitting phosphor Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ was synthesized using a high‐temperature solid‐state reaction under a reductive atmosphere. The X‐ray diffraction measurements indicate that a pure phase Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ can be obtained for low doping concentration of Eu²⁺. The phosphor has a strong absorption in the range 270–420 nm with a maximum at ~340 nm and blue emission in the range 400–500 nm with chromatic coordination of (0.152, 0.045). The optimal doping concentration is ~0.24. In addition, the luminescence properties of the as‐synthesized phosphor were evaluated by comparison with those of Ca₁₂Al₁₄O₃₂Cl₂:Eu²⁺ and the commercially available phosphor BaMgAl₁₀O₁₇:Eu²⁺. The emission intensity of Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ was ~72% that of BaMgAl₁₀O₁₇:Eu²⁺ under excitation at λ = 375 nm. The results indicate that Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ has potential application as a near‐UV‐convertible blue phosphor for white light‐emitting diodes.     

Photoluminescence properties of a new orange–red‐emitting Sm3+–La3SbO7 phosphor

The antimonate compound La₃SbO₇ has high chemical stability, lattice stiffness and thermal stability. Orange–red‐emitting antimonate‐based phosphors La₃SbO₇:xSm³⁺ (x = 0.02, 0.05, 0.08, 0.10, 0.15, 0.20 and 0.25) were synthesized. The phase structure and photoluminescence properties of these phosphors were investigated. The emission spectrum obtained on excitation at 407 nm contained exclusively the characteristic emissions of Sm³⁺ at 568, 608, 654 and 716 nm, which correspond to the transitions from ⁴G_5/2 to ⁶H_5/2, ⁶H_7/2, ⁶H_9/2 and ⁶H_11/2 of Sm³⁺, respectively. The strongest emission was located at 608 nm due to the ⁴G_5/2→⁶H_7/2 transition of Sm³⁺, generating bright orange–red light. The critical quenching concentration of Sm³⁺ in La₃SbO₇:Sm³⁺ phosphor was determined as 10% and the energy transfer between Sm³⁺ was found to be through an exchange interaction. The International Commission on Illumination chromaticity coordinates of the La₃SbO₇:0.10Sm³⁺ phosphors are located in the orange–red region. The La₃SbO₇:Sm³⁺ phosphors may be potentially used as red phosphors for white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Luminescence study of Dy or Ce activated LiCaBO3 phosphor for γ‐ray and C5+ ion beam irradiation

The photoluminescence and thermoluminescence characteristics of rare earths (Dy or Ce) activated LiCaBO₃ phosphors have been studied. Phosphors were synthesized by modified solid state synthesis. The phosphors were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) and thermoluminescence (TL) for structural, morphological and luminescence studies. Dy³⁺ activated LiCaBO₃ shows emission at 486 and 577 nm due to ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transition, respectively, whereas the PL emission spectra of Ce³⁺ activated LiCaBO₃ phosphor shows a broad band peaking at 432 nm, which is due to the transition from 5d level to the ground state of the Ce³⁺ ion. The thermoluminescence study was also carried out for both these phosphors for γ‐ray irradiation and carbon beam irradiation. Linearity was studied for a 0.4–3.1 Rad dose γ‐rays. Linear behaviour over this dose range was observed. Gamma ray‐irradiated phosphors were shown to be negligible fading upon storage. All the samples were also studied for 75 MeV C⁵⁺ ion beam exposure in the range of 3.75 × 10¹² – 7.5 × 10¹³ ion cm^–2 fluence. In addition to this, trapping parameters of all the samples were also calculated using Chen's peak shape method. Copyright © 2015 John Wiley & Sons, Ltd.     

A promising RVO4:Eu3+,Li+@SiO2 (R = Gd,Y and Gd/Y) red‐emitting phosphor with improved luminescence (cd/m2) and colour purity for optical display applications

Red emission intensity was optimized in three stages, by investigating the effects of: (i) host composition (Gd, Y and Gd/Y), (ii) codoping Li⁺ as a sensitizer and, finally, (iii) with a SiO₂ shell coating as a protecting layer. Lanthanide vanadate powder phosphors were synthesized using a modified colloidal precipitation technique. The effects of SiO₂ coating on phosphor particles were characterized using scanning electron microscopy (SEM)‐EDAX, transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and photoluminescence (PL) measurements. An improvement in the PL intensity on Li codoping was due to improved crystallinity, which led to higher oscillating strengths for the optical transitions, and also a lowering of the inversion symmetry of Eu³⁺ ions. Red emission intensity due to ⁵D₀ → ⁵D₂ transition of the phosphor Y_0.94VO₄:Eu³⁺_0.05,Li⁺_0.01 was enhanced by 22.28% compared with Y_0.95VO₄:Eu³⁺_0.05, and was further improved by 58.73% with SiO₂ coating. The luminescence intensity (I) and colour coordinates (x, y) of the optimized phosphor Y_0.94VO₄:Eu³⁺_0.05,Li⁺_0.01@SiO₂, where I = 13.07 cd/m² and (x = 0.6721, y = 0.3240), were compared with values for a commercial red phosphor (Y₂O₂S:Eu³⁺), where I = 27 cd/m² and (x = 0.6522, y = 0.3437). The measured colour coordinates are superior to those of the commercial red phosphor, and moreover, match well with standard NTSC values (x = 0.67, y = 0.33). Copyright © 2015 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.     

Synthesis and luminescence characterization of a new yellowish‐orange phosphor: Ba2B10O17:Sm3+

A new yellowish‐orange emitting phosphor, Ba₂B₁₀O₁₇:Sm³⁺ for use as a white light‐emitting diode (W‐LED) was synthesized by a solid‐state reaction method. The X‐ray diffraction results indicated that a pure Ba₂B₁₀O₁₇ material was obtained. As a potential yellowish‐orange luminescent material for W‐LEDs, the Ba₂B₁₀O₁₇:Sm³⁺ phosphor could be excited effectively by near‐ultraviolet (n‐UV) light and exhibited yellowish‐orange emission centered at 560 nm corresponding to the ⁴G_5/2 → ⁶H_5/2 transition of Sm³⁺ ions. The optimum concentration of Sm³⁺ ions in Ba₂B₁₀O₁₇, critical transfer distance (Ra) and concentration quenching mechanism of the presented phosphor were investigated. Moreover, CIE chromaticity coordinates and color purity performance of the Ba₂B₁₀O₁₇:Sm³⁺ phosphor were also discussed. The present work suggests that the Ba₂B₁₀O₁₇:Sm³⁺ phosphor has potential as a type of yellowish‐orange emitting phosphor. Copyright © 2016 John Wiley & Sons, Ltd.     

Sr2ZnWO6:Eu3+,Bi3+,Li+: a potential white‐emitting phosphor for near‐ultraviolet white light‐emitting diodes

A series of Sr₂ZnWO₆ phosphors co‐doped with Eu³⁺, Bi³⁺ and Li⁺ were prepared using the Pechini method. The samples were tested using X‐ray diffraction and luminescence spectroscopy. The results show that the samples can be effectively excited by near‐ultraviolet (UV) and UV light. The introduction of Bi³⁺ and Li⁺ significantly enhances the fluorescence emission of Sr₂ZnWO₆:Eu³⁺ and changes the light emitted by the phosphors from bluish‐green to white. When excited at 371 nm, Sr_2–x–zZn_1–yWO₆:xEu³⁺,yBi³⁺,zLi⁺ (x = 0.05, y = 0.05, z = 0.05, 0.1 and 0.15) samples emit high‐performance white light. Intense red–orange emission is also observed when excited by UV light. The obtained phosphor is a potential white‐emitting phosphor that could meet the needs of excitation sources with near‐UV chips. In addition, this phosphor might have promising application as a red–orange emitting phosphor for white light‐emitting diodes based on UV light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Co‐precipitation synthesis and luminescence properties of K2TiF6:Mn4+ red phosphors for warm white light‐emitting diodes

K₂TiF₆:Mn⁴⁺ red phosphors with different Mn⁴⁺ doping concentrations were obtained using the co‐precipitation method. X‐Ray diffraction, scanning electron microscopy, Raman spectra, Fourier transform infrared spectroscopy, photoluminescence excitation and emission spectra and decay curves were used to characterize the properties of K₂TiF₆:Mn⁴⁺ phosphors. Under excitation at 470 nm, an intense red emission peak around 631 nm corresponding to the ²E_g–⁴A₂ transition of Mn⁴⁺ was observed for 2.48 mol% K₂TiF₆:Mn⁴⁺ phosphors and was used as the optimum doping concentration. The excellent luminescent properties of K₂TiF₆:Mn⁴⁺ suggest that this material might be a promising red phosphor for generating warm white light in phosphor‐converted white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Comparison of luminescence property of gamma‐ray irradiated Tb3+‐doped and Ce3+ co‐doped potassium halide single crystals

Single crystals of KCl and KBr singly and doubly doped with Tb³⁺ and Ce³⁺, respectively, were successfully grown using the Bridgeman technique. This work reports the comparative luminescence behavior and optical absorption characterization of non‐irradiated and γ‐ray‐irradiated single crystals of these materials. The existing defect and the defect created by γ‐ray irradiation were monitored by optical absorption spectra. The excitation and emission spectra of these materials were measured at room temperature with a spectrofluorometer and the pertaining results were compared. The F‐band comparison was made when bleached with F‐light for 2 mins. The trap‐level changes in KCl and KBr when it is singly and doubly doped enabled us to draw conclusions on the nature of the defect and on the recombination processes involved.     

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.     

Study of luminescence and effect of Dy3+ on NaMgSO4Cl:Ce chlorosulphate phosphor

Chlorosulphate NaMgSO₄Cl phosphor doped with Ce³⁺ and co‐doped by Dy³⁺ prepared by the wet chemical method was studied for its photoluminescence and thermoluminescence (TL) characteristics. The emission spectrum of Ce³⁺ shows dominant peaks at 346 nm (excitation 270 nm) due to 5d → 4f transition. Efficient energy transfer occurs from Ce³⁺ → Dy³⁺ ions. Dy³⁺ emission at 485 nm and 576 nm is due to ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ion respectively. The TL glow curves of NaMgSO₄Cl:Ce and Ce,Dy have been recorded for various concentrations at a heating rate of 2 °C/s irradiated by γ‐rays at a dose rate of 0.995 kGy/h for 1 Gy, which peaks at about 241 °C and 247‐312 °C respectively. Further, in changing the concentration level, the general structure of the intensity is found to increase. The main property of this phosphor is its sensitivity even for low concentrations of rare earth ions and low γ‐ray dose. There is still scope for higher doses of γ‐radiation. The phosphor presented may be used as a lamp phosphor as well as for TL studies. Copyright © 2014 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.