Preparation and Long Persistence Red Luminescence of M0.2Ca0.8TiO3∶Pr3+(M=Mg2+,Sr2+,Ba2+,Zn2+)

M0.2Ca0.8TiO3∶Pr3 (M=Mg2 , Sr2 , Ba2 , Zn2 ) long persistence red phosphors were prepared by solid state reaction. The influence of the partially replacing Ca2 in CaTiO3 with Mg2 , Sr2 , Ba2 , Zn2 on the excitation spectra, the emission spectra and the long persistence properties were studied. The results suggest that certain quantity of Mg2 , Sr2 , Ba2 , Zn2 which partially replace Ca2 can enhance the luminescent intensity and prolong the afterglow persistence of the samples. The intensity of Mg0.2Ca0.8TiO3∶Pr3 is above all of the samples. Take Mg0.2Ca0.8TiO3∶Pr3 as the basic sample, the influence of Pr3 concentrations(C(Pr3 )) on the long afterglow properties were also studied. The results suggest that when the C(Pr3 ) is 0.10%(mol fraction) the intensity of the sample is the highest. The excitation spectra of all these samples show broad band spectra ranging from 300～500 nm peaking at about 342 nm. The emission spectra also exhibit a broad band peaking at 613 nm(CaTiO3∶Pr3 is 612 nm). XRD research indicates that the crystalline phases change due to the replacement of divalent metal ions.The research on the thermoluminescence spectra of Mg0.2Ca0.8TiO3∶Pr3 indicates that the peak is at 107.35 ℃ and the depth of the trap energy is about 0.852 eV.     

Enhancement of luminescence and afterglow in Ca0.8Zn0.2TiO3:Pr3+ by Nb5+ substitution for Ti4+

Nb5+ doped Ca0.8Zn0.2TiO3:Pr3+ red long afterglow phosphors were synthesized by solid-state reaction methods. X-ray diffraction, photoluminescence spectroscopy and thermally stimulated spectrometry were used to investigate the effects of Nb5+ content on the crystal characteristics and luminescent properties of Ca0.8Zn0.2Ti1-xNbxO3:Pr3+ phosphors. The results showed that the addition of a small quantity of Nb5+ had negligible effect on the crystal characteristics of Ca0.8Zn0.2Ti1-xNbxO3:Pr3+, but it could change the trapping parameters (the depth of trap, frequency factors and the concentration of trapped charges at t=0) of Ca0.8Zn0.2Ti1-xNbxO3:Pr3+ phosphors, and then led to the enhance-ment of red fluorescence and phosphorescence at 612 nm originating from 1D2→3H4 transition of Pr3+. Both of the red fluorescence intensity and afterglow time reached the largest values in the sample of Ca0.8Zn0.2Ti1-xNbxO3:Pr3+ with x=0.05. The afterglow time of Ca0.8Zn0.2Ti0.95Nb0.05O3:Pr3+ phosphors lasted for over 24 min (≥1 mcd/m2) when the excited source was cut off.     

（Zn, Ca） Solid-Solution Behavior and Its Effect on Luminescence Properties in Ca1-x Znx TiO3 ： 0.002Pr^3＋ Phosphors

Nominal composition of Ca1-xZnxTiO3 ： 0. 002Pr^3 ＋ （x = 0. 000 - 0. 200） phosphors were prepared by conventional solid reaction route. XRD and PL measurements were used to investigate the solid-solution structure and luminescence properties of Zn-doped Ca1-xZnxTiO3：0.002Pr^3＋ phosphors. The effect of solid-solution structure formed by substitution between Ca^2 ＋ and Zn^2＋ ions on the luminescent properties was analyzed. The results reveal that, with the increase of Zn substitution content below 0.010, lattice parameters and the intensity of excitation peak at both 260 and 330 nm as well as the corresponding 610 nm emission intensity are monotonously decreased quickly in a similar tendency. Also, the evolution of luminescence intensity and crystal cell parameters against Zn doping concentration are in good agreement. Above results are closely related with the structure change within Ca1- xZnxTiO3：0.002Pr^3＋ solid-solution phase formed by the Zn ions substitution for the Ca sites. Present study reveals that the solid-solution structure formed by substitution between Ca^2＋ and Zn^2＋ ions has significant effect on the luminescence properties of single phase Ca1-xZnxTiO3：0.002Pr^3＋ phosphors.     

Investigation on luminescence properties of Ln^3＋ doped Sr3EuMgSi2O8 （Ln=Dy, Er, Ho）

The luminescent properties of Sr2.97MgSi2O8:Eu2+0.01 phosphors were investigated with different Ln3+0.02(Ln3+:Dy3+,Er3+,Ho3+) co-dopants. The co-dopants had no influence on both the structure of the lattice and the position of the emission peak. However, the afterglow properties of samples were enhanced with different co-dopants. The afterglow duration of the Dy3+ co-doped sample was longer than that of the others. Furthermore, the co-doping samples had stronger thermoluminescence (TL) intensity and therefore longer afterglow duration. At last, the self-reduction of Eu3+→Eu2+ was observed in an silicate compound of Sr3-xMgSi2O8:xEu phosphor in air condition. This is the first time to show a blue long afterglow phosphor synthesized avoiding reducing atmosphere.     

Co-Precipitation Synthesis and Spectral Characteristics of Long Afterglow Phosphor Y2O2 S： Sm^3＋, Mg^2＋ , Ti^4＋

Y2O2S：Sm^3＋, Mg^2＋, Ti^4＋ phosphor was synthesized by co-precipitation method. The crystalline structure of all synthesized phosphors was investigated by XRD. The result showed that all synthesized phosphors had a hexagonal crystal structure, which was the same as Y2O2S. The emission spectrum and excitation spectrum were measured, and the effect of Sm^3 ＋ molar ratio on the spectra was discussed. The emission spectra of the phosphors showed three emission peaks due to typical transitions of Sm^3 ＋ （4G5/2→6HJ ,J = 5/2, 7/2, 9/2）, and the emission peaks at 606 nm was stronger than others. With the increase of Sm^3 ＋ molar ratio, the emission intensity was strengthened. The excitation peaks were ascribed to the representative energy transition 4f→4f of Ti^4＋ phosphor prepared by co-precipitation method was Sm^3＋ ions. The results indicated that the Y2O2S ： Sm^3＋ , Mg^2＋ , an efficient long afterglow phosphor.     

Effect of Ho^3＋ Ion on Luminescent Property of CaGaeS4：Eu^2＋

The afterglow luminescent property and thermo-luminescence (TL) of CaGa2S4：Eu^2 , Ho^3 were systemateally investigated. The afterglow of Eu and Ho Co-doped CaGa2S4 shows a broadband emission at 552 nm, which is the same as that of Eu doped CaGa2S4 only. And the decay behavior of CaGa2S4 Eu^2 , Ho^3 was investigated, which shows that CaGa2S4: Eu^2 , Ho^3 is a phosphor with long after-glow, whereas the CaGazS4:Eu^2 is a phosphor with-out long afterglow. Comparison of TL curves and 3D-TL emission spectra of CaGa2S4:Eu^2 ,Ho^3 and Ca-C, a2S4:Eu^2 show that a new trap center is produced at about 80℃, which is the basic reason of CaGazS4:Eu^2 ,Ho^3 with long afterglow.     

Preparation and Luminescence Properties of the New Long Phosphorescent Phosphors Ba1-x Cax Al2O4 ： Eu^2＋ , Dy^3＋

New long phosphorescent phosphors Ba1-x CaxAl2O4:Eu^2 , Dy^3 with tunable color emission were prepared and studied. The emission spectra show that the tuning range of the color emission of the phosphors is between 498 and 440 nm, which is dependent on x, under the excitation of UV. The wavelength of the afterglow increases with the increasing of x until x equals 0.6. The XRD patterns show that the single phase limit in the phosphors is below x value of 0.4.The Thermolumineseence spectra were measured to investigate the traps created by the doping of Dy^3 .     

Preparation and Characterization of Red Luminescent Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ Nanophosphor

Nanophosphor with the nominal composition of Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ （CZTOPN） was synthesized at relatively low temperature by the sol-gel method. Metal ions were dispersed by citric acid in ethylene glycol solvent and then react with Ti（OC4H9）4 to form sol and gel. The decomposition process of the precursor, and crystallization and particle size of CZTOPN were examined by thermal analysis （TG-DSC）, powder X-ray diffraction （XRD）, and scan election microscopy （SEM）. Results of TG-DSC and XRD reveal that the composition of Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ changes with the sintering temperature. SEM data indicate that the diameter of particles is under 50 nm even if the sintering temperature increases to 1000 ℃. In contrast to a solid state reaction, the excitation spectra of samples synthesized by the sol-gel method shift blue about 10 nm and the emission intensity at 617 nm increases significantly.     

Synthesis of Long Afterglow Phosphors MAI204：Eu^2＋ , Dy^3＋ （M=Ca, Sr, Ba） by Microemulsion Method and Their Luminescent Properties

Long afterglow phosphors MAl2O4：Eu^2＋ , Dy^3＋ （M = Ca, Sr, Ba） were synthesized by microemulsion method, and their crystal structure and luminescent properties were compared and investigated. XRD patterns of samples indicate that phosphors CaAl2O4：Eu^2＋, Dy^3＋ and SrAl2O4 ： Eu^2＋, Dy^3＋ are with monoelinie crystal structure and phosphor BaAl2O4：Eu^2＋ , Dy^3＋ is with hexagonal crystal structure. The wide range of excitation spectrum of phosphors MAl2O4： Eu^2 ＋ , Dy^3＋ （M = Ca,Sr, Ba） indicates that the luminescent materials can he excited by light from ultraviolet ray to visible light and the maximum emission wavelength of phosphors MAl2O4：Eu^2＋ , Dy^3＋ （M = Ca, Sr, Ba） is found mainly at λem of 440 nm （M = Ca）, 520 nm （M = Sr） and 496 nm （M = Ba） respectively, the corresponding colors of emission light are blue, green and eyna-green respectively. The afterglow decay tendency of phosphors can he summarized as three processes： initial rapid decay, intermediate transitional decay and very long slow decay. Afterglow decay curves coincide with formula I = At^ - n, and the sequence of afterglow intensity and time is Sr 〉 Ca 〉 Ba.     

Synthesis of Long Afterglow Phosphor CaAl2Si2O8 ：Eu^2＋, Dy^3＋ via Sol-Gel Technique and Its Optical Properties

The long afterglow phosphor CaAl2Si2O8：Eu^2＋ , Dy^3＋ was prepared by a sol-gel method. The sol-gel process and the structure of the phosphor were investigated by means of X-ray diffraction analysis （XRD）. It is found that the single anorthite phase formed at about 1000 %, which is 300 % lower than that required for the conventional solid state reaction. The obtained phosphor powders are easier to grind than those of solid state method and the partical size of phosphor has a relative narrow distribution of 200 to 500 nm. The photoluminescence and afterglow properties of the phosphor were also characterized. An obvious blue shift occurs in the excitation and emission spectra of phosphors obtained by sol-gel and solid state reaction methods. The change of the fluorescence spectra can be attributed to the sharp decrease of the crystalline grain size of the phosphor resulted from the sol-gel technique.     

Effect of different dopants on the long lasting phosphorescence behavior of CaTiO_3：Pr~（3＋）

In order to improve the luminescence properties of CaTiO3:Pr3+, a series of CaTiO3:Pr3+, such as CaTi0.97Nb0.03O3:Pr3+, Ca0.8Zn0.2TiO3: Pr3+, Ca0.8Zn0.2Ti0.97Nb0.03O3:Pr3+ and B3+-doped Ca0.8Zn0.2Ti0.97Nb0.03O3: Pr3+ were prepared through conventional solid state reaction method. The results of the photoluminescence excitation and emission spectra showed that all the samples emitted red phosphorescence at 612 nm originating from 1D2 to 3H4 emission of Pr3+ under the 337 nm excitation. When examined by the X-ray diffraction (XRD), all the samples presented a predominant phase of CaTiO3 (JCPDS# 42-423) except Zn2+-doped samples which also revealed another phase of Zn2Ti3O8 (JCPDS# 73-579). The results of the afterglow decay curves showed that co-doping Zn2+ ions, Nb5+ ions or adding a small amount of B3+ into Ca0.8Zn0.2Ti0.97Nb0.03O3:Pr3+ were effective in improving the photoluminescence properties of CaTiO3:Pr3+ phosphor. Thermoluminescence results showed that the trap existing in all the samples was the same as in CaTiO3:Pr3+ and doping singly Nb5+ or Zn2+ hardly changed the trap depth but co-doping Nb5+ and Zn2+ could modify the trapping level from 0.63 to 1.26 eV distinctively. In addition, adding a certain amount of B3+ into CTO-PZN could also deepen the trap depth.     

Structure and luminescent properties of luminous polypropylene fiber based on Sr2MgSi2OT：EU^2＋,Dy^3＋

The luminous polypropylene fiber based on long afterglow luminescent material Sr2MgSi2O7：Eu^2＋,Dy^3＋was prepared by melt-spinning process. Micro-morphology, phase composition, crystal structure, spectral features and afterglow properties of the lu-minescent fiber were tested and analyzed. The results indicated that the fiber had independent superposition phase features of both Sr2MgSi2O7：Eu2＋,Dy3＋and polypropylene. The range of its excitation wavelength was located between 250-450 nm;therefore, the luminescent fiber could be excited by ultraviolet or visible light. It could emit blue light of 460 nm wavelength after excitation, which was caused by the 5d-4f transition of Eu^2＋ions within the host lattice. The initial luminescent intensity was more than 0.8 cd/m^2, and afterglow life lasted 7 h. The afterglow decay was composed of rapid-decaying and slow-decaying processes, and the decay charac-teristics depended on the depth and concentration of trap level in the Sr2MgSi2O7：Eu^2＋,Dy^3＋.     

Upconversion luminescence of Y2O3：Er^3＋ ,Yb^3＋ nanoparticles prepared by a homogeneous precipitation method

Y2O3： Er^3＋, Yb^3＋ nanoparticles were synthesized by a homogeneous precipitation method without and with different concentrations of EDTA 2Na. Upconversion luminescence spectra of the samples were studied under 980 nm laser excitation. The results of XRD showed that the obtained Y2O3：Er^3＋,Yb^3＋ nanoparticles were of a cubic structure. The average crystallite sizes calculated were in the range of 28-40 nm. Green and red upconversion emission were observed, and attributed to ^2H11/2,^4S3/2→^4I15/2 and ^4F9/2→^4I15/2 transitions of the ion, respectively. The ratio of the intensity of green emission to that of red emission drastically changed with a change in the EDTA 2Na concentration. In the sample synthesized without EDTA, the relative intensity of the green emission was weaker than that of the red emission. The relative intensities of green emission increased with the increased amount of EDTA 2Na used. The possible upconversion luminescence mechanisms were discussed.     

Effects of Host Doping on Spectral and Long-Lasting Properties of Sm^3＋ -Doped Y2O2S

Gd- or Lu-doped long afterglow red phosphor Y2O2S：Sm^3＋ was synthesized using the high temperature flux fusion method. The obtained phosphors were analyzed using X-ray diffraction to determine the crystal structure, and the phase analyses show that the product is in single phase. The luminescence spectra and decay curve were measured on a Hitachi F-4500 fluorescence spectrophotometer. The decay time was determined on an ST-900PM weak light photometer. The analyses show that host doping of Lu improves both luminescence and decay time of the materials. The concentration of doped Lu and Sm was varied in order to determine the optimal condition and to synthesize the product with the best properties. The mechanism of the long afterglow was also briefly discussed.     

Synthesis of Long Afterglow Photoluminescent Materials Sr2MgSi2O7：Eu^2＋,Dy^3＋ by Sol-Gel Method

Long afterglow photoluminescent materials Sr2MgSi2O7 dopeo With Eu^2 ,Dy^3 were prepared by sol-gel method. The synthesized samples were characterized by X-ray diffraction. The excitation spectrum, emission spectrum and long decay curve were measured and analyzed. XRD pattern indicates that phosphor is with Sr2MgSi2O7 crystal structure. The wide range of excitation wavelength indicates that luminescent material can be excited by light from ultraviolet ray to visible light. The main peak of emission spectrum is located at 466nm. Sample excited by visible light can emit bright blue light, and the afterglow time lasts more than 8h.     

Luminescent properties of blue long-lasting phosphorescence phosphors Sr6Al18Si2O37：Eu2＋,RE3＋

A series of novel blue long-lasting phosphorescence phosphors Sr6A118Si2037：Eu^2＋,RE^3＋ （RE3＋=Ho^3＋, Gd^3＋, Dy^3＋ and Pr^3＋） were prepared by the conventional high-temperature solid-state reaction in a reductive atmosphere. Their properties were systemati- cally investigated utilizing X-ray diffraction （XRD）, photoluminescence, phosphorescence and thermoluminescence （TL） spectra. The phosphors emitted blue light that was related to the emission of E~＋ due to 5d-4f transition. Bright blue long-lasting phosphorescence （LLP） could be observed after the excitation source was switched off. For the optimized sample, the blue long-lasting phosphores- cence could last for nearly 4 h in the light perception of the dark-adapted human eye （0.32 mcd/m2）. The effects of RE3＋ ions on phosphorescence properties of the phosphors were studied, and the results showed that the co-doping of RE^3＋ ions greatly enhanced the intensity of the peak around 315 K which was related to the long lasting phosphorescence of the phosphors at room temperature and consequently improved the performance of the blue phosphorescence such as intensity and persistent time.     

Temperature-Dependent Emission of Pr^3＋ -Doped LaB3O6 under Vacuum Ultraviolet Excitation

The vacuum ultraviolet （VUV） luminescent properties of Pr^3＋ -activated LaB3O6 were investigated with highenergetic synchrotron radiation from 20 to 300 K. In the emission spectra, the parity-forbidden 4f^2→4f^2 and parity-allowed 4f5d→4f^2 transitions were observed simultaneously. In addition, it was also observed that the intensity of 4f5d→4f^2 emission bands increased relative to the intensity of 4f^2→4f^2 emissions with increasing temperature. The thermal equilibrium model of energy levels was employed with respect to the lowest 4f5d state and ^1S0 state of LaB3O6：Pr^3＋ , as a result of which the fitted curve had a good agreement with the experiment values, which clarified the physical nature of temperature-dependent emission characteristics of Pr^3＋ in LaB3O6.     

Eu2＋ and Dy3＋ codoped （Ca,Sr）7（SiO3）6Cl2 highly efficient yellow phosphor

Eu2+ and Dy3+ codoped(Ca,Sr)7(SiO3)6Cl2 yellow phosphors were successfully synthesized by self-flux method. The structure, morphology and photoluminescence properties were investigated by X-ray diffraction(XRD), scanning electron microscopy(SEM) and photoluminescence spectra. The as-prepared phosphor showed a broad emission spectrum centered at 550 nm for Eu2+single-doped phosphor, while located at 548–544 nm for the Eu2+, Dy3+ codoped samples under excitation at 380 nm light. The emission intensity was greatly improved when Dy3+ was doped into the(Ca,Sr)7(SiO3)6Cl2:Eu2+ system. The composition-optimized sample with 3 mol.% of Dy3+ and constant 10 mol.% of Eu2+ exhibited a 220% PL enhancement compared to the phosphor with 10 mol.% Eu2+ single-doped. Meanwhile, it was found that the quantum efficiency of phosphor namely(Ca,Sr)7(SiO3)6Cl2:3 mol.% Dy3+, 10 mol.% Eu2+ could get up to 24.6%. The synthesized yellow-emitting(Ca,Sr)7(SiO3)6Cl2:Dy3+,Eu2+ is a promising candidate as high-efficiency yellow phosphor for NUV-excited white LEDs.     

Investigation on Preparation and Fluorescence Properties of Oxy-Fluoride Glass Co-Doped with Er^3＋ and Yb^3＋

The glass sample based on the composition of 45PbF2-45GeO2-10WO3 co-doped with Yb^3 /Er^3 was prepared by the fusion method in two steps : melted at 950℃ for 20～25min then annealed at 380℃ for 4 h. Through the V-prism it is found that the refractive index of host glass and the sample are 1.517 and 1.65 respectively. The transmittance was observed by using the ultraviolet-visible-infrared spectrometer in the wavelength range from 0.35 to 2.5μm. The transmittance of the host glass is beyond 73%. That of the sample is beyond 50% and there are characteristic absorption peaks of rare-earth ions. The emission spectrum was measured by using the Hitachi F-4500 fluorescent spectrometer pumped by 980nm semiconductor laser. There are a strong emission peak at 530 nm and a weak peak at 650 nm.     

Preparation of Stable CaS： Eu^2＋ , Tm^3＋ Phosphor

Different fluxes were used to synthesize long persistence phosphors, calcium sulfides activated by Eu^2 and Tm^3 , by convenient solid-state method. The phosphor using NH4F as a flux has good crystallinity and large particle size, its stability against water and other atmospheric components is enhanced, and its afterglow is longer and fluorescent inten-sity is more intense than those of the phosphor using NH4Cl as flux. Their PL intensities varied with time in moist air were measured, no remarkable change was found for those prepared with NH4F flux in contrast with NH4Cl as flux. So using NH4F as flux is a good method to enhance the stability of alkaline earth sulfides.