Thermoluminescence mechanism in rare-earth-doped magnesium tetra borate phosphors

Magnesium tetra borate (MTB) doped with rare earths (REs) was prepared by the solid state sintering technique. Among the different RE dopants studied in this phosphor, gadolinium-doped phosphors resulted in a dosimetric peak at a relatively higher temperature. The thermoluminescence (TL) emission spectra of RE-doped MTB showed characteristic RE ³⁺ emissions. Electron paramagnetic resonance measurements were carried out in these phosphors to identify the defect centers formed during gamma irradiation and to establish a mechanism for the TL process. Signals corresponding to (BO ₃)^2?, O _v^? were seen upon irradiation which vanished on annealing at 250 °C, showing the role of these centers in the TL process. The thermal activation energies calculated based on the decay of these signals matched well with those calculated on the basis of the usual conventional method showing the validity of the mechanism of TL.     

Thermoluminescence excitation spectroscopy: A versatile technique to study persistent luminescence phosphors

A versatile new facility to study photoionization processes in impurity doped compounds is presented. In this new facility monochromatic light is coupled to a thermoluminescence reader, enabling a fully automated recording of glow curves as a function of photon excitation wavelength. It provides detailed information on the mechanism of trap filling preceding persistent luminescence. The technique is first demonstrated with a study on Lu₂SiO₅:Ce³⁺ and then applied to commercial modern day double lanthanide doped SrAl₂O₄:Eu²⁺,Dy³⁺, Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺, CaAl₂O₄:Eu²⁺,Nd³⁺; and to the classical ZnS:Cu⁺ persistent luminescence phosphors. The presented data provide new insight into the mechanism of persistent luminescence.     

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.     

Red,Yellow, Blue and Green Emission from Eu<Superscript>3+</Superscript>, Dy<Superscript>3+</Superscript> and Bi<Superscript>3+</Superscript> Doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>nano-Phosphors

Rare earth elements (RE = Eu³⁺& Dy³⁺)and Bi³⁺ doped Y₂O₃ nanoparticles were synthesized by urea hydrolysis method in ethylene glycol, which acts as reaction medium as well as a capping agent, at a low temperature of 140 °C,followed by calcination of the obtained product. Transmission electron microscope (TEM) images reveals that ovoid shaped Y₂O₃ nanoparticles of around 22–24 nm size range were obtained in this method. The respective RE and Bi³⁺ doped Y₂O₃ precursor nanoparticles when heated at 600 and 750 °C, retains the same shape as that of the as-synthesized Y₂O₃ precursor samples. From EDAX spectra, the incorporation of RE ions into the host has been studied. XRD pattern reveals the crystalline nature of the heated nanoparticles and indicate the absence of any impurity phase other than cubic Y₂O₃.However, the as-synthesized nanoparticles were highly amorphous without the presence of any sharp XRD peaks. Photoluminescence study suggests that the synthesized samples could be used as red (Eu³⁺), yellow (Dy³⁺), blue and green (Bi³⁺)emitting phosphors.     

Thermoluminescent properties of Eu and RE co-doped phosphors CaGa2S4:Eu, RE (RE=Ln, excluding Pm, Eu and Lu)

The thermo-luminescence (TL) of rare earth ions RE³⁺ (RE=Ln, excluding Pm, Eu and Lu) co-doped phosphors CaGa₂S₄:Eu²⁺, RE³⁺ was studied between room temperature and 300 °C, and 3D thermo-luminescence of the phosphors were measured from room temperature to 400 °C. The basic material CaGa₂S₄:Eu²⁺, showed at least two bands in the TL glow curve. Changing the auxiliary activator RE³⁺ (rare earth ion), intensities and the positions of the TL glow curve peaks were affected significantly. For the phosphors with long afterglow, auxiliary activator such as Ce³⁺, Pr³⁺, Gd³⁺, Tb³⁺, Ho³⁺, or Y³⁺ created some new defects in these compounds at lower trap levels and enhanced their TL intensities. The Nd³⁺ or Er³⁺ auxiliary activator only enhanced TL intensities to a low extent, so these two phosphors have short persistent luminescence at room temperature. TL intensities of La³⁺, Sm³⁺, Tm³⁺ or Yb³⁺ co-doped phosphors were suppressed greatly and no afterglow was shown. The relationship between auxiliary activators and corresponding thermo-luminescence curves of phosphors CaGa₂S₄:Eu²⁺, RE³⁺ are discussed in detail. According to our results, suitable activation energy and enough high corresponding trap density are necessary for the phosphor with long afterglow.     

Photoluminescence of Eu single doped and Eu/Dy codoped Sr2Al2SiO7 phosphors with long persistence

This paper reports the preparation of long persistent Sr₂Al₂SiO₇:Eu²⁺ and Sr₂Al₂SiO₇:Eu²⁺, Dy³⁺ phosphors and the comparison of their photoluminescent properties. The silicate phosphors prepared by solid-state reaction routine showed a broad blue emission peaking at 484 nm when activated by UV illumination. Such a bluish-green emission can be attributed to the intrinsic 4f-5d transitions of Eu²⁺. After the UV source was switched off, long persistent phosphorescence could be observed by naked eyes for both samples in darkness. Afterglow measurements revealed that Eu/Dy codoped phosphor possesses better afterglow properties than the Eu single doped one, since the maximum lifetime (τ_max=99 s) of the photons calculated from the decay profile is much larger than that of the Eu single doped phosphor (τ_max=82 s). TSL results suggested that the difference in afterglow properties was caused by the difference in the electron traps within the crystal lattice. For Eu/Dy codoped phosphor, the doping of Dy ions produced electron traps with trap depth of 0.52 eV, which is suitable and therefore leads to good persistence. However, in the case of Eu single doped phosphor, the trap depth is 0.88 eV, which is really too deep an energy barrier to overcome, and therefore a poor persistence was observed in the experiment.     

Influences of Doping and Annealing on the Structural and Photoluminescence Properties of Y2O3 Nanophosphors

This paper reports the structural and optical properties of rare earth doped and codoped yttrium oxide nanophosphors. Dysprosium (Dy³⁺) and Terbium (Tb³⁺) doped and codoped yttrium oxide (Y₂O₃) phosphors were prepared by combustion synthesis method and subsequently annealed to high temperature to eliminate the hydroxyl group (?OH) and to get more crystallinity. The formation of compounds was confirmed by the X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR). The diffuse reflectance spectra (DRS) of doped and codoped Y₂O₃ powder phosphors were measured and it is observed that the absorption edge of the doped samples is shifted towards blue region with respect to undoped sample. The bandgap of the prepared samples were evaluated with the help of Kubelka-Munk function using Diffuse Reflectance Spectra (DRS) and an increase in bandgap was observed with the decrease in crystallite size. A strong characteristics emission from Tb³⁺ and Dy³⁺ ions was identified and the influence of doping concentration and annealing temperature on photoluminescence properties was systematically studied. Transfer of energy was observed in dysprosium–terbium codoped Y₂O₃ nanophosphor at room temperature from Dy³⁺ ions toTb³⁺ ions.     

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.     

Synthesis and characterization of Ce doped silica (SiO2) nanoparticles

A series of silica doped with different mol percentages of Ce³⁺ concentration was synthesized using a sol-gel method to determine the dependence of photoluminescence wavelengths and intensity on the concentrations of the dopants. Sol-gel glasses are porous networks that have been densified through chemical processing and heat treatment. Rare-earths (REs) are insoluble in silica; due to this insolubility RE ions in silicate glasses enter as network modifiers and compete for non-bridging oxygen in order to complete their coordination. The morphological, structural, thermal and optical properties of the phosphors were characterized by X-ray diffraction, scanning electron microscopy, UV-vis absorption, photoluminescence, thermogravimetric analyses and differential scanning calorimeter. Silica (SiO₂) gel containing Ce³⁺ ions was sputter coated with Au (gold) in order to monitor surface morphology of the samples. The highest emission intensity was found for the sample with a composition of 0.5 mol% Ce³⁺. Cerium doped silica glasses had broad blue emission corresponding to the ²D_3/2-²F_J transition at 448 nm but exhibited apparent concentration quenching above concentrations of 0.5 mol% Ce³⁺.     

Temperature and wavelength dependent trap filling in M2Si5N8:Eu (M=Ca,Sr, Ba) persistent phosphors

The evaluation of persistent phosphors is often focused on the processes right after the excitation, namely on the shape of the afterglow decay curve and the duration of the afterglow, in combination with thermoluminescence glow curve analysis. In this paper we study in detail the trap filling process in europium-doped alkaline earth silicon nitrides (Ca₂Si₅N₈:Eu, Sr₂Si₅N₈:Eu and Ba₂Si₅N₈:Eu), i.e., how the persistent luminescence can be induced. Both the temperature at which the phosphors are excited and the spectral distribution of the excitation light on the ability to store energy in the phosphors' lattices are investigated. We show that for these phosphors this storage process is thermally activated upon excitation in the lower 5d excited states of Eu²⁺, with the lowest thermal barrier for europium doped Ca₂Si₅N₈. Also, the influence of co-doping with thulium on the trap filling and afterglow behavior is studied. Finally there exists a clear relation between the luminescence quenching temperature and the trap filling efficiency. The latter relation can be utilized to select new efficient 5d–4f based afterglow phosphors.     

Encapsulating MAl2O4:Eu2+, Dy3+ (M = Sr,Ca, Ba) phosphors with triethanolamine to enhance water resistance

Traditional aluminates phosphors with persistent luminescence are chemically unstable to water or moisture. Thus, how to improve the water-resistance of these phosphors is becoming a key issue in their practical applications. In this work, a series of alkaline earth aluminate phosphors including MAl₂O₄:Eu²⁺, Dy³⁺ (M = Sr, Ca, Ba) have been prepared by a co-precipitation synthesis and postannealing approach, using 8-hydroxyquinoline and sodium oxalate as precipitants. The samples before and after encapsulation were well characterized by means of XRPD, FESEM, FT-IR, TGA-DTG and PL techniques as well as water resistance measurements. The precipitants involved can react with Al³⁺ and Sr²⁺ (or Ca²⁺, Ba²⁺) to form complex compounds in aqueous solution, which further convert into porous phosphors by postannealing method under reducing atmosphere. Next, triethanolamine encapsulation at room temperature was conducted onto their surfaces to improve the water resistance. The results reveal that the encapsulation of aluminate phosphors with triethanolamine can effectively enhance the water resistance, and minimally affect on persistent phosphorescence.     

Eu3+ emission in SrAl2B2O7 based phosphors

Eu³⁺ doped SrAl₂B₂O₇ phosphors were fabricated by the wet method. The structures of the phosphors were characterized by XRD. The doping content of Eu³⁺ ions in SrAl₂B₂O₇:Eu³⁺ phosphors are 1%, 4%, 6%, 8%, 10% (molar fraction), respectively. Luminescence properties were analyzed by measuring the excitation and photoluminescence spectra. The luminescent properties of SrAl₂B₂O₇:Eu³⁺ phosphors are discussed. It is shown that from 4% to 6% of doping content of Eu³⁺ ions under 392 nm excitation in SrAl₂B₂O₇:Eu³⁺ phosphors is optimum.     

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.     

Crystal growth and optical properties of Cr3+, Er3+, RE3+: Gd3Ga5O12 (RE=Tm,Ho, Eu) for mid-IR laser applications

In this paper we report on the optical properties of triply Cr³⁺, Er³⁺, and RE³⁺ (RE=Tm, Ho, Eu) doped Gd₃Ga₅O₁₂ crystals that were grown by the Czochralski method. Optical absorption, near-infrared (NIR), and mid-infrared (mid-IR) fluorescence spectra were characterized for the fabricated crystals and corresponding luminescence decay measurements under 654 nm excitation were also carried out. Based on the analysis of energy transfer process between Er and RE (RE=Tm, Ho, Eu) ions, the energy transfer efficiency (ETE) values were evaluated, correspondingly. From the spectral data of all the studied crystals, it is observed that the co-doped Cr³⁺ ion highly increases the absorption pump power and the three kinds of co-doped RE³⁺ ions depopulate the Er:⁴I_13/2 energy level effectively. The spectral analysis shows that titled rare earth doped crystals are promising materials for ～3.0 μm mid-IR laser applications and among them Cr,Er,Eu:GGG is relatively more suitable due to its excellent optical properties compared with others.     

Photoluminescence spectra of rare earth doped CaGa2S4 single crystals

Six kind CaGa₂S₄ single crystals doped with different rare earth (RE) elements are grown by the horizontal Bridgman method, and their photoluminescence (PL) spectra are measured in the temperature range from 10 to 300 K. The PL spectra of Ce or Eu doped crystals have broad line shapes due to the phonon assisted 4f-5d transitions. On the other hand, those of Pr³⁺, Tb³⁺, Er³⁺ or Tm³⁺ doped samples show narrow ones owing to the 4f-4f transitions. The assignments of the electronic levels are made in reference to the reported data of RE 4f multiplets observed in same materials.     

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).     

Rare earth doped lithium titanate (Li2TiO3) for potential phosphor applications

Lithium titanate ceramics doped with three rare earth (RE) ions namely Eu³⁺, Dy³⁺ and Tb³⁺ were synthesized and their photoluminescence (PL) properties were investigated. PL spectra of Eu doped sample showed peaks corresponding to the ⁵D₀→⁷F_j (j=0, 1, 2, 3 and 4) transitions under 230 nm excitation. Strong red emission coming from the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ ion suggested the presence of the dopant ion in a highly asymmetric environment. Dy doped samples showed the Dy³⁺ emission characteristic due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions. Their relative intensity ratios also suggested the presence of asymmetric environment around the metal ion. In case of the Tb³⁺ doped sample blue-green emission corresponding to the ⁵D₄→⁷F_j (j=6, 5 and 4) transitions was seen. The fluorescence lifetimes of Eu³⁺, Dy³⁺ and Tb³⁺ ions were found to be 645, 900 and 740 μs, respectively. PL intensity of the individual rare earth doped samples was compared with commercial red and green phosphors. It was found that the emission from Eu doped titanate sample was 46% of the commercial red phosphor and in case of the Tb samples it was 30% when excited at 230 nm. However, the synthesized Eu doped titanate sample showed better color purity as compared to the commercial phosphor. The titanate host was doped with all the three rare earths to get white light emission from the system. The individual rare earth ion content was optimized so as to get a near white light emission. The color coordinates of the triple doped systems were evaluated and plotted on the CIE x–y diagram. Our results suggest that lithium titanate has enough potential to be a phosphor material.     

Luminescence characteristics of Eu2+ activated Ca2SiO4 Sr2SiO4 and Ba2SiO4 phosphorsfor white LEDs

<正>This paper investigates the luminescence characteristics of Eu²⁺ activated Ca₂SiO₄,Sr₂SiO₄ and Ba₂SiO₄ phosphors. Two emission bands are assigned to the f-d transitions of Eu²⁺ ions doped into two different cation sites in host lattices,and show different emission colour variation caused by substituting M²⁺ cations for smaller cations.This behaviour is discussed in terms of two competing factors of the crystal field strength and covalence.These phosphors with maximum excitation of around 370 nm can be applied as a colour-tunable phosphor for light-emitting diodes（LEDs） based on ultraviolet chip/phosphor technology.     

Emission analysis of Li6LuY(BO3)3:Tb3+,Dy3+ phosphors

In this paper, we present the synthesis and luminescence properties of Tb³⁺ and Dy³⁺-doped lithium lutetium yttrium borate (Li₆LuY(BO₃)₃) phosphors. We have adopted the well-known solid state reaction method for the synthesis of these phosphors. The emission intensities of the synthesized phosphors were found to reach their maximum, when doped by 1 mol% of Tb³⁺ and 3 mol% of Dy³⁺, beyond which emission intensities decrease due to concentration quenching. The homogeneous phase, crystalline structure and uniform morphology of the synthesized phosphors were confirmed by X-ray diffraction analysis (XRD) and Scanning electron microscopy (SEM). The X-ray and UV–VIS-induced luminescence, decay time and CIE chromaticity were investigated for the synthesized phosphors.The X-ray induced integrated light yield was measured to be 82% for Li₆LuY(BO₃)₃:Tb³⁺ (LLYBO) and 59% for Li₆LuY(BO₃)₃:Dy³⁺ of that of commercially available X-ray imaging material; Gd₂O₂S:Tb³⁺ (Gadox).LLYBO:Tb³⁺ phosphor displayed five major emission bands that correspond to ⁵D_j → ⁷F_j transitions. The 1931 Commission Internationale de l'Eclairage (CIE) chromaticity coordinates were also measured.     

Luminescent properties of Eu2+and Dy3+ ions in Ba4Al2O7 phosphor for solid state lighting

In this paper we report the combustion synthesis of rare earth (RE=Eu, Dy) doped Ba₄Al₂O₇ phosphors. Prepared phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), CIE color co-ordinates and their photoluminescence (PL) properties were also investigated. In case of Ba₄Al₂O₇: Eu²⁺, the emission spectra show unique band centered at 495 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺, and PL emission spectra of Dy³⁺ ion under 348 nm excitation give two bands centered at 478 nm (blue) and 575 nm (yellow), which originate from the transitions of ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The results indicate that the Eu²⁺ and Dy³⁺ activated Ba₄Al₂O₇ phosphor could find application in solid state lighting.