Influence of co-doping different rare earth ions on CaGa2S4: Eu, RE(RE=Ln) phosphors

Photoluminescent phosphors CaGa₂S₄: Eu²⁺, RE³⁺ (RE³⁺ including all rare earth ions except for Sc³⁺, Pm³⁺, Eu³⁺ and Lu³⁺) were prepared by sintering at high temperature in a reductive atmosphere, and their luminescent properties were studied intensively. The influences of co-doping rare earth ions on their luminescent properties were also investigated. No remarkable differences were found from excitation spectra of co-doped phosphors CaGa₂S₄: Eu²⁺, RE³⁺ in contrast with that of phosphor CaGa₂S₄: Eu²⁺, but there were a few differences in emission spectra of Ce³⁺, Pr³⁺ or Ho³⁺ co-doped phosphors. Phosphors CaGa₂S₄: Eu²⁺, RE³⁺ (RE=Ce, Pr, Gd, Tb, Ho and Y) had persistent afterglow, and very short afterglow was shown for Nd³⁺ or Er³⁺ co-doped phosphors, but no long afterglow appeared when auxiliary activator was La³⁺, Sm³⁺, Dy³⁺, Tm³⁺ or Yb³⁺. Among the phosphors with long-lasting phosphorescence, in our experiments, CaGa₂S₄: Eu²⁺, Ho³⁺ had the longest and the highest brightness long yellow afterglow. Thermo-luminescence of all co-doped phosphors was measured to find the answer of different influences from different rare earth auxiliary activators.     

Phosphorescent and thermoluminescent properties of SrAl2O4:Eu,Dy phosphors prepared by solid state reaction method

Long persistent SrAl₂O₄:Eu²⁺ phosphors co-doped with Dy³⁺ were prepared by the solid state reaction method. The main diffraction peaks of the monoclinic structure of SrAl₂O₄ were observed in all the samples. The broad band emission spectra at 497 nm for SrAl₂O₄:Eu²⁺, Dy³⁺ were observed and the emission is attributed to the 4f⁶5d¹ to 4f⁷ transition of Eu²⁺ ions. The samples annealed at 1100–1200 °C showed similar broad TL glow curves centered at 120 °C. The similar TL glow curves suggest that the traps responsible for them are similar. The long afterglow displayed by the phosphors annealed at different temperatures, may be attributed to the Dy³⁺ ions acting as the hole trap levels, which play an important role in prolonging the duration of luminescence.     

Photoluminescence and afterglow behavior of Eu, Dy and Eu, Dy in Sr3Al2O6 matrix

This paper reports the photoluminescence and afterglow behavior of Eu²⁺ and Eu³⁺ in Sr₃Al₂O₆ matrix co-doped with Dy³⁺. The samples containing Eu²⁺ and Eu³⁺ were prepared via solid-state reaction. X-ray diffraction (XRD), photo luminescent spectroscope (PLS) and thermal luminescent spectroscope (TLS) were employed to characterize the phosphors. The comparison between the emission spectra revealed that Sr₃Al₂O₆ phosphors doped with Eu²⁺, Dy³⁺ and Eu³⁺, Dy³⁺ showed different photoluminescence. The phosphor doped with Eu³⁺, Dy³⁺ showed an intrinsic f-f transition generated from Eu³⁺, with two significant emissions at 591 and 610 nm. However, the phosphor doped with Eu²⁺, Dy³⁺ revealed a broad d-f emission centering around 512 nm. After the UV source was turned off, Eu²⁺, Dy³⁺ activated Sr₃Al₂O₆ phosphor showed excellent afterglow while Eu³⁺, Dy³⁺ activated phosphor almost showed no afterglow. Thermal simulated luminescence study indicated that the persistent afterglow of Sr₃Al₂O₆: Eu²⁺, Dy³⁺ phosphor was generated by suitable electron traps formed by the co-doped rare-earth ions (Dy³⁺) within the host.     

Thermoluminescence of rare earth activated CdSO4, SrSO4 and BaSO4

The thermoluminescence (TL) of rare earth (RE) activated sulfates of Cd, Sr and Ba was studied above room temperature. Many of the phosphors prepared exhibit an extremely bright TL following X-irradiation (most notably with Sm, Eu, Tb, Dy and Tm dopants), having an efficiency comparable to that of the highest sensitivity phosphors available for TL dosimetry, and exhibiting activator-induced glow peaks between 405 and 480°K. In a given lattice, the RE³⁺ ions produce a characteristic glow peak at the same temperature (independent of the particular RE ion), whereas Eu²⁺ produces a single glow peak at a different temperature. A decrease in glow peak temperature with increasing interatomic spacing was observed in the homologous SrSO₄-BaSO₄ system - this shift being most pronounced in the Eu²⁺ -doped materials. TL emission spectra were obtained for trivalent Sm, Tb, Dy and Tm and for divalent Eu in these sulfates (and also in CaSO₄).     

Eu red long afterglow in Y2O2S:Ti, Eu phosphor through afterglow energy transfer

Eu,Ti co-doped Y₂O₂S:0.03Ti,0.03Eu phosphors and single Eu or Ti doped Y₂O₂S phosphors were prepared and their luminescent properties were investigated in detail by photoluminescence (PL) spectra, long afterglow spectra and thermoluminescence spectra measurements. The results showed that Y₂O₂S:Ti,Eu phosphors possess orange-red afterglow color with afterglow time above 5 h. The reddish afterglow color, which corresponds to a set of linear Eu³⁺ emissions at low-energy range (540-630 nm), was demonstrated to come from the energy transfer process from yellow Ti afterglow emissions, the proposed energy transfer mechanism may well explain the Eu³⁺ afterglow emission.     

Effect of RE as a co-dopant in long-lasting phosphorescence CdSiO3:Mn (RE=Y, La, Gd, Lu)

Effect of RE³⁺ as a co-dopant in long-lasting phosphorescence CdSiO₃:Mn²⁺ (RE=Y, La, Gd, Lu) has been investigated. A longer orange emitting phosphorescence phenomenon was observed in the co-doped CdSiO₃:Mn²⁺,RE³⁺ phosphors after exciting with ultraviolet (UV) light. The luminescence properties, including photoluminescence (PL) spectra and thermoluminescence (TL) spectra, as well as the afterglow decay curves, were studied. The results revealed that one of the origins of the improvement is due to nonequivalent substitution to produce more e-traps, and energy transfer from Gd³⁺ to Mn²⁺ to boost the performance of CdSiO₃:Mn²⁺,Gd³⁺. Role of RE³⁺ co-doped into CdSiO₃:Mn²⁺ matrix and the possible long-lasting phosphorescence process are discussed in this paper.     

Synthesis and characterization of BaAl2O4:Eu co-doped with different rare earth ions

Combustion method was used in this study to prepare BaAl₂O₄:Eu²⁺ phosphors co-doped with different trivalent rare-earths (Re³⁺=Dy³⁺, Nd³⁺, Gd³⁺, Sm³⁺, Ce³⁺, Er³⁺, Pr³⁺ and Tb³⁺) ions at an initiating temperature of 600 °C. The phosphors were annealed at 1000 °C for 3 h. As confirmed from the X-ray diffraction (XRD) data, both as prepared and post annealed samples crystallized in the well known hexagonal structure of BaAl₂O₄. All samples exhibited bluish-green emission associated with the 4f⁶5d¹→4f⁷ transitions of Eu²⁺ at ∼500 nm. Although the highest intensity was observed from Er³⁺ co-doping, the longest afterglow (due to trapping and detrapping of charge carriers) was observed from Nd³⁺ followed by Dy³⁺ co-doping. The traps responsible for the long afterglow were studied using thermoluminescence (TL) spectroscopy.     

Luminescence investigations on sulfate apatite Na6(SO4)2FCl:RE (RE=Dy, Ce or Eu) phosphors

A new phosphor in the Cl-F system doped with Dy, Ce and Eu has been reported. Characterization of this phosphor using XRD, PL and TL techniques is described. Polycrystalline Na₆(SO₄)₂FCl:Dy; Na₆(SO₄)₂FCl:Ce and Na₆(SO₄)₂FCl:Eu phosphors prepared by a solid state diffusion method have been studied for their X-ray diffraction, photoluminescence (PL) and thermoluminescence (TL)characteristics. The PL excitation and emission spectra of phosphors were obtained. Dy³⁺ emission in the host at 475 and 570 nm is observed due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transition, respectively, whereas the PL emission spectra of Na₆(SO₄)₂FCl:Ce phosphor shows the Ce³⁺ emission at 322 nm due to 5d→4f transition of Ce³⁺ ion. In Na₆(SO₄)₂FCl:Eu lattice, Eu²⁺ as well as Eu³⁺ emissions are observed. The emission of europium ion in this compound exhibits the blue as well as red emission. The TL glow curves of the same compounds have the simple structure with a prominent peak at 150, 175 and 200 °C. TL response, fading, reusability and trapping parameters of the phosphors are also studied. The TL glow curves of γ-irradiated Na₆(SO₄)₂FCl sample show one glow peak indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak are calculated using Chen’s half width method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. The intensity of the TL glow peaks increases with increase of the added γ-ray dose to the samples.     

Dosimetric properties of rare earth doped LiCaBO3 thermoluminescence phosphors

Lithium Calcium borate (LiCaBO₃) polycrystalline thermoluminescence (TL) phosphor doped with rare earth (RE³⁺) elements has been synthesized by high temperature solid state diffusion reaction. The reaction has produced a very stable crystalline LiCaBO₃:RE³⁺ phosphors. Among these RE³⁺ doped phosphors thulium doped material showed maximum TL sensitivity with favorable glow curve shape. TL glow curve of gamma irradiated LiCaBO₃:Tm³⁺ samples had shown two major well-separated glow peaks at 230 and 430 °C. The glow peak at 430 °C is almost thrice the intensity of the glow peak at 230 °C. The TL sensitivity of the phosphor to gamma radiation was about eight times that of TLD-100 (LiF). Photoluminescence and TL emission spectra showed the characteristic Tm³⁺ peaks. TL response to gamma radiation dose was linear up to 10³ Gy. Post-irradiation TL fading on storage in room temperature and elevated temperatures was studied in LiCaBO₃:Tm³⁺ phosphor.     

Luminescence properties of Tm co-doped Sr2Si5N8:Eu red phosphor

The Sr₂Si₅N₈:Eu²⁺ phosphors, both undoped and doped with Tm³⁺, were synthesized by high temperature solid-state method. The XRD pattern shows that only Sr₂Si₅N₈ phase is formed whatever Tm³⁺ was doped or not. The peak positions of both phosphors are centered at 612 nm which is assigned to the 4f⁶5d→4f⁷ transition of Eu²⁺. It implies that the crystal field, which affects the 5d electron states of Eu²⁺, is not changed dramatically after the phosphor is doped with Tm³⁺. The afterglow time is about 10 min after Tm³⁺ ion is introduced into the phosphor. The concentration of Tm³⁺ has little influence on the afterglow time of the phosphor. The depths of trap energy level of the two phosphors were calculated based on the TL spectra. The depths of Sr₂Si₅N₈:Eu²⁺ and Sr₂Si₅N₈:Eu²⁺, Tm³⁺ are 1.75 and 1.01 eV, respectively.     

Low-temperature thermoluminescence in CaGa2S4:Eu

In the last years many insulating and semiconducting materials activated with rare-earth elements were found to exhibit phosphorescence and thermoluminescence properties, and are attracting increasing interest due to the variety of application of long-lasting phosphors. In this work we studied the phosphorescence decay and thermoluminescence properties of CaGa₂S₄:Eu²⁺ as a function of temperature in the 9-325 K range. The comparison between spectra recorded as a function of time delay from the excitation pulse at different temperatures indicates that long-lasting emissions peaked at about 2.2 eV occurs at Eu²⁺ sites. Thermoluminescence glow curve is characterized by five components at 69, 98, 145, 185 and 244 K. Experimental data are discussed in the framework of generalized order of kinetic model and allow to estimate the activation energies of trapping defects. The origin of glow components at 69, 98, 145 and 244 K is correlated to trapping defects induced by Eu²⁺ doping, while the component at 185 K is attributed to a continuous distribution of defects.     

Luminescent properties of (Y,Gd)BO3:Bi,RE (RE=Eu, Tb) phosphor under VUV/UV excitation

Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors were prepared and their luminescent properties under vacuum ultraviolet (VUV)/UV excitation were investigated. Strong red emission for (Y,Gd)BO₃:Bi³⁺,Eu³⁺ and strong green emission for (Y,Gd)BO₃:Bi³⁺,Tb³⁺ are observed under VUV excitation from 147 to 200 nm with a much broader excitation region than that of single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃ phosphor. Strong emissions are also observed under UV excitation around 265 nm where as nearly no luminescence is observed for single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃. The luminescence enhancement of Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors is due to energy transfer from Bi³⁺ ion to Eu³⁺ or Tb³⁺ ion not only in the VUV region but also in the UV region. Besides, host sensitization competition between Bi³⁺ and Eu³⁺ or Tb³⁺ is also observed. The investigated phosphors may be preferable for devices with a VUV light 147-200 nm as an excitation source such as PDP or mercury-free fluorescent lamp.     

Effects of non-stoichiometry on crystallinity, photoluminescence and afterglow properties of Sr2MgSi2O7:Eu, Dy phosphors

Eu²⁺, Dy³⁺ co-doped Sr₂MgSi₂O₇ phosphors with deficient, stoichiometric or excess amounts of silicon are prepared by solid-state reaction. XRD and SEM results indicate that all the samples studied are found to be free from impurities and samples with SiO₂ excess possess better crystallinity and larger grain size. Photoluminescence reveals that the position of Eu²⁺ emission is not changed with various compositions. However, both photoluminescence intensity and afterglow properties are increased by an incorporation of excess SiO₂ and are decreased by SiO₂ deficiency. The thermoluminescence results show that the corresponding increase or decrease in afterglow is associated with trap density, but no change in trap depth. The underlying reason of photoluminescence and afterglow enhancement is discussed.     

Afterglow mechanism and thermoluminescence of red-emitting CaS:Eu,Pr phosphor with incorporated Li ion upon visible light irradiation

This paper reports on the afterglow mechanism and thermoluminescence (TL) of a red-emitting CaS:Eu²⁺,Pr³⁺ phosphor with incorporated Li⁺ ion upon irradiation by visible light (D₆₅ lamp). In the TL glow curve of the CaS:Eu²⁺,Pr³⁺ phosphor, a TL peak was observed near 120 °C. The luminescence center of the CaS:Eu²⁺,Pr³⁺ phosphor was the Eu²⁺ ion and the trap depth of the CaS:Eu²⁺,Pr³⁺ phosphor with the cation vacancy (Trap 1) which formed by incorporation of the Pr³⁺ ion was 0.202 eV. A cation vacancy (Trap 2) was formed by incorporation of the Li⁺ ion in the CaS:Eu²⁺,Pr³⁺ phosphor. In the TL glow curve of the CaS:Eu²⁺,Pr³⁺ phosphor with incorporated Li⁺ ion, two TL peaks were observed near 120 and 200 °C. The TL luminance of the CaS:Eu²⁺,Pr³⁺ phosphor with incorporated Li⁺ ion increased with an increase in the initial Li/Ca atomic ratio. The two TL peaks moved to the high-temperature side with an increase in heating rate. The cation vacancy (Trap 2) calculated from the Hoogenstraaten method was 0.118 eV. The afterglow time of the CaS:Eu²⁺,Pr³⁺ phosphor with incorporated Li⁺ ion was prolonged by generation of a shallow trap.     

Thermoluminescent and stuctural properties of BaAl2O4:Eu,Nd,Gdphosphors prepared by combustion method

BaAl₂O₄:Eu²⁺,Nd³⁺,Gd³⁺ phosphors were prepared by a combustion method at different initiating temperatures (400–1200 °C), using urea as a comburent. The powders were annealed at different temperatures in the range of 400–1100 °C for 3 h. X-ray diffraction data show that the crystallinity of the BaAl₂O₄ structure greatly improved with increasing annealing temperature. Blue-green photoluminescence, with persistent/long afterglow, was observed at 498 nm. This emission was attributed to the 4f⁶5d¹–4f⁷ transitions of Eu²⁺ ions. The phosphorescence decay curves were obtained by irradiating the samples with a 365 nm UV light. The glow curves of the as-prepared and the annealed samples were investigated in this study. The thermoluminescent (TL) glow peaks of the samples prepared at 600 °C and 1200 °C were both stable at ∼72 °C suggesting that the traps responsible for the bands were fixed at this position irrespective of annealing temperature. These bands are at a similar position, which suggests that the traps responsible for these bands are similar. The rate of decay of the sample annealed at 600 °C was faster than that of the sample prepared at 1200 °C.     

Eu/Tb ions co-doped white light luminescence Y2O3 phosphors

Y₂O₃:Eu³⁺, Tb³⁺ phosphors with white emission are prepared with different doping concentration of Eu³⁺ and Tb³⁺ ions and synthesizing temperatures from 750 to 950 °C by the co-precipitation method. The resulted phosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. The results of XRD indicate that the crystallinity of the synthesized samples increases with enhancing the firing temperature. The photoluminescence spectra indicate the Eu³⁺ and Tb³⁺ co-doped Y₂O₃ phosphors show five main emission peaks: three at 590, 611 and 629 nm originate from Eu³⁺ and two at 481 and 541 nm originate from Tb³⁺, under excitation of 250-320 nm irradition. The white light luminescence color could be changed by varying the excitation wavelength. Different concentrations of Eu³⁺ and Tb³⁺ ions were induced into the Y₂O₃ lattice and the energy transfer from Tb³⁺→Eu³⁺ ions in these phosphors was found. The Commission International de l’Eclairage (CIE) chromaticity shows that the Y₂O₃:Eu³⁺, Tb³⁺ phosphors can obtain an intense white emission.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

A novel blue-emitting long-lasting proyphosphate phosphor Sr2P2O7:Eu,Y

By introducing the Y³⁺ into Sr₂P₂O₇:Eu²⁺, we successfully prepared a kind of new phosphor with blue long-lasting phosphorescence by the high-temperature solid-state reaction method. In this paper, the properties of Sr₂P₂O₇:Eu²⁺,Y³⁺ were investigated utilizing XRD, photoluminescence, luminescence decay, long-lasting phosphorescence and thermoluminescence (TL) spectra. The phosphor emitted blue light that was related to the 4f⁶5d¹-⁸S_7/2 transition of Eu²⁺. The bright blue phosphorescence could be observed by naked eyes even 8 h after the excitation source was removed. Two TL peaks at 317 and 378 K related to two types of defects appeared in the TL spectrum. By analyzing the TL curve the depths of traps were calculated to be 0.61 and 0.66 eV. Also, the mechanism of LLP was discussed in this report.     

Photoluminescence investigations of Zn2SiO4 co-doped with Eu and Tb ions

Zinc silicate phosphors co-doped with Eu³⁺ ions and also with both Eu³⁺ and Tb³⁺ ions were prepared by high temperature solid state reaction in air or reducing atmosphere. The luminescence characteristics of the prepared phosphors were investigated. While in the samples prepared in air, Eu³⁺ emission was found to be dominant over Tb³⁺ emission, in the samples prepared in reducing atmosphere, intense Eu²⁺ emission at 448 nm was found to be predominant over narrow Tb³⁺ emission. Luminescence studies showed that Eu³⁺ ions occupy asymmetric sites in Zn₂SiO₄ lattice. The intense f-f absorption peak of Eu³⁺ at 395 nm observed in these phosphors suggests their potential as red emitting phosphors for near ultra-violet light emitting diodes.     

Combustion synthesis of Sr3MgSi2O8:Eu and Sr2MgSi2O7:Eu phosphors

Sr₃MgSi₂O₈:Eu²⁺ and Sr₂MgSi₂O₇:Eu²⁺ phosphors find uses in applications such as plasma display panel (PDP), solid-state lighting, longafter glow. Preparation of these phosphors by a modified combustion synthesis is described in this paper. As-prepared samples did not show photoluminescence. After reducing the samples at 900 °C, characteristic Eu²⁺ emission was observed. Preparation of these phosphors by using similar methods helped clarifying various results obtained for Sr₃MgSi₂O₈:Eu²⁺ by different investigators.