Synthesis and luminescence investigation of RE (Eu, Tb and Ce)-doped lithium silicate (Li2SiO3)

Synthesis and photoluminescence (PL) investigations of lithium metasilicate doped with Eu³⁺, Tb³⁺ and Ce³⁺ were carried out. PL spectra of Eu-doped sample showed peaks corresponding to the ⁵D₀→⁷F_j (j=1, 2, 3 and 4) transitions under ultraviolet excitation. Strong red emission coming from the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ ion suggested the presence of the dopant ion in structurally disordered environment. Tb³⁺-doped silicate sample showed blue-green emission corresponding to the ⁵D₄→⁷F_j (j=6, 5 and 4) transitions. Ce-doped sample under excitation from UV, showed a broad emission band in the region 350-370 nm with shoulders around 410 nm. The fluorescence lifetimes of Eu³⁺ and Tb³⁺ ions were found out to be 790 and 600 μs, respectively. For Ce³⁺, the lifetime was of the order of 45 ns. PL spectra of the europium- and terbium-doped samples were compared with commercial red (Y₂O₃:Eu³⁺) and green (LaPO₄:Tb³⁺) phosphors, respectively. It was found that the emission from the doped silicate sample was 37% of the commercial phosphor in case of the Tb-doped sample and 8% of the commercial phosphor in case of the Eu-doped sample.     

Enhanced luminescence of Tb by efficient energy transfer from Ce in Sr2B5O9Cl host

Ce³⁺ and Tb³⁺ co-doped Sr₂B₅O₉Cl phosphors with intense green emission were prepared by the conventional high-temperature solid-state reaction technique. A broad band centered at about 315 nm was found in phosphor Sr₂B₅O₉Cl: Ce³⁺, Tb³⁺ excitation spectrum, which was attributed to the 4f-5d transition of Ce³⁺. The typical sharp line emissions ranging from 450 to 650 nm were originated from the ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) transitions of Tb³⁺ ions. The photoluminescence (PL) intensity of green emission from Tb³⁺ was enhanced remarkably by co-doping Ce³⁺ in the Tb³⁺ solely doped Sr₂B₅O₉Cl phosphor because of the dipole-dipole mechanism resonant energy transfer from Ce³⁺ to Tb³⁺ ions. The energy transfer process was investigated in detail. In light of the energy transfer principles, the optimal composition of phosphor with the maximum green light output was established to be Sr_1.64Ce_0.08Tb_0.1Li_0.18B₅O₉Cl by the appropriate adjustment of dopant concentrations. The PL intensity of Tb³⁺ in the phosphor was enhanced about 40 times than that of the Tb³⁺ single doped phosphor under the excitation of their optimal excitation wavelengths.     

Luminescence properties of Ce and Tb co-activated ZnAl2O4 phosphor

In this study, a solution combustion method was used to prepare green emitting Ce³⁺–Tb³⁺ co-activated ZnAl₂O₄ phosphor. The samples were annealed at 700 °C in air or hydrogen atmosphere to improve their crystallinity and optical properties. X-ray diffraction study confirmed that both as-prepared and post-preparation annealed samples crystallized in the well known cubic spinel structure of ZnAl₂O₄. An agglomeration of irregular platelet-like particles whose surfaces were encrusted with smaller spheroidal particles was confirmed by scanning electron microscopy (SEM). The fluorescence data collected from the annealed samples with different concentrations of Ce³⁺ and Tb³⁺ show the enhanced green emission at 543 nm associated with ⁵D₄→⁷F₅ transitions of Tb³⁺. The enhancement was attributed to energy transfer from Ce³⁺ to Tb³⁺. Possible mechanism of energy transfer via a down conversion process is discussed. Furthermore, cathodoluminescence (CL) intensity degradation of this phosphor was also investigated and the degradation data suggest that the material was chemically stable and the CL intensity was also stable after 10 h of irradiation by a beam of high energy electrons.     

Luminescence in LaBaB9O16 prepared by combustion synthesis

LaBaB₉O₁₆ phosphors activated by various ions belonging to ns², 3dⁿ and 4fⁿ configurations were prepared by combustion synthesis. Phosphors’ synthesis and luminescence spectra are reported. Most of the activators displayed intense characteristic emission. Pr³⁺→Gd³⁺, Ce³⁺→Tb³⁺, Ce³⁺→Dy³⁺, Ce³⁺→Mn²⁺ and Bi³⁺→Mn²⁺ energy transfers were also observed. In particular, Ce³⁺→Tb³⁺ energy transfer leads to an efficient green emitting phosphor.     

White-light long-lasting phosphorescence from Tb-activated Y2O2S phosphor

The white-light long-lasting phosphors Y₂O₂S:Tb³⁺, Sr²⁺ or/and Zr⁴⁺ were prepared and studied. The white-light afterglow emission after the irradiation with 254 nm UV are composed of the blue light emission and the yellowish-green light emission, originating from the transitions of ⁵D₃→⁷F₅, ⁵D₄→⁷F₅ in Tb³⁺ when the Tb³⁺ concentration is not higher than 0.3 at%. The codoped Sr²⁺ and Zr⁴⁺ ions act as trap-creating ions. The afterglow can last over 21 min in the dark for Y₂O₂S:Tb³⁺0.3%, Sr²⁺4%, Zr⁴⁺4% after irradiation by 254 nm ultraviolet light. Y₂O₂S:Tb³⁺ may be a promising material for the development of white-light long-lasting phosphor since the Tb³⁺ has a high luminescent efficiency and the dominant excitation band of 4f →5d is located at 220-300 nm.     

Emission analysis of Tb:MgAl2O4 powder phosphor

This paper reports the emission analysis of green-emitting Tb³⁺-doped MgAl₂O₄ phosphors. Uniformity of the phase of the Tb³⁺-doped MgAl₂O₄ phosphor has been checked by X-ray diffraction (XRD) technique and show common bands existing in the results of Fourier transform infrared (FT-IR). This phosphor exhibits weak blue, orange emissions and a strong emission at λ_exci=350 nm. The blue and green-orange emissions are ascribed to ⁵D₃→⁷F_J and ⁵D₄→⁷F_J (where J=3-6) transitions of Tb³⁺ ions, respectively. These phosphors have shown a strong, more prominent green emission from ⁵D₄→⁷F₅ at 543 nm. The results have indicated that MgAl₂O₄:Tb³⁺ could be a potential candidate as agreen-emitting powder phosphor.     

Heat-treatment-induced luminescence degradation in Tb-doped CePO4 nanorods

CePO₄:Tb nanorods were synthesized via a simple wet-chemical route. The as-synthesized CePO₄:Tb nanorods present high photoluminescence efficiency due to an efficient energy transfer form Ce³⁺ to Tb³⁺. However, heat treatment at 150 °C in air leads to a significant decrease of photoluminescence. X-ray photoelectron spectroscopy and excitation spectra revealed the oxidation of Ce³⁺ to Ce⁴⁺ in the heat-treatment process, which should be responsible for significant photoluminescence degradation due to the breakage of Ce³⁺→Tb³⁺ energy transfer. This conclusion is further supported by atmosphere and size effects of photoluminescence of CePO₄:Tb under the heat treatment.     

Enhanced luminescent properties of Y3Al5O12:Tb,Ce phosphor prepared by spray pyrolysis

Yttrium aluminum garnet (YAG) particles doped with Tb³⁺ or double doped with Tb³⁺ and Ce³⁺ were prepared by spray pyrolysis and characterized by photo- and cathode-luminescence. It was tried to incorporate a broad band of Ce³⁺ activator into the line peaks of Tb³⁺ in YAG host without the reduction of emission intensity. Ce-codoped YAG:Tb particles showed a broad band emission due to the d-f transition of Ce³⁺ and a reduction in the intensity of emission peaks due to ⁵D₃-⁷F_j (j=3, 4, 5, 6) transition of Tb³⁺ when they were excited by the ultraviolet light of 270 nm. These results supported that an effective energy transfer occurs from Tb³⁺ to Ce³⁺ in YAG host. Codoping Ce³⁺ ions greatly intensified the excitation peak at 270 nm for the emission at 540 nm of Tb³⁺, which means that more lattice defects, involving in the energy absorption and transfer to Tb³⁺, are formed by the Ce³⁺ codoping. The finding gives a promising approach for enhancing the luminescence efficiency.     

Sol-gel preparation and photoluminescence property of YBO3:Eu/Tb nanocrystalline thin films

YBO₃:Eu³⁺/Tb³⁺ nanocrystalline thin films were successfully deposited onto quartz glass substrates by Pechini sol-gel dip-coating method, using rare-earth nitrates and boric acid as starting materials. The crystal structure, morphology, chemical composition and photoluminescence property of the films were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy and fluorescence spectrophotometer. The results of XRD, AFM, XPS and FTIR revealed that the films were composed of spherical YBO₃:Eu³⁺/Tb³⁺ nanocrystals with average grain size of 80 nm. The YBO₃:Eu³⁺ film exhibited strong orange emission at 595 nm and red emission at 615 nm, which were, respectively ascribed to the (⁵D₀→⁷F₁) and (⁵D₀→⁷F₂) transitions of Eu³⁺. The YBO₃:Tb³⁺ film showed dominant green emission at 545 nm due to the ⁵D₄-⁷F₅ transition of Tb³⁺.     

Enhancement of red spectral emission intensity of Y3Al5O12:Ce phosphor via Pr co-doping and Tb substitution for the application to white LEDs

We have enhanced color-rendering property of a blue light emitting diode (LED) pumped white LED with yellow emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) phosphor using addition of Pr and Tb as a co-activator and host lattice element, respectively. Pr³⁺ addition to YAG:Ce phosphor resulted in sharp emission peak at about 610 nm through ¹D₂→³H₄ transition. And when Tb³⁺ substituted Y³⁺ sites, Ce³⁺ emission band shifted to a longer wavelength due to larger crystal field splitting. Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and (Y_1−xTb_x)₃Al₅O₁₂:Ce³⁺ phosphors were coated on blue LEDs to fabricate white LEDs, respectively, and their color-rendering indices (CRIs, R_a) were measured. As a consequence of the addition of Pr³⁺ or Tb³⁺, CRI of the white LEDs improved to be R_a=83 and 80, respectively. Especially, blue LED pumped (Y_0.2Tb_0.8)₃Al₅O₁₂:Ce³⁺ white LED showed both strong luminescence and high color-rendering property.     

Quenching of thermo-stimulated photo-ionization by energy transfer in CaAl4O7: Tb, Ce

Crystal fibers of Ce³⁺ and Tb³⁺ singly doped and co-doped CaAl₄O₇ were grown by the LHPG method. Photoluminescence, excitation spectra and photoconduction were measured. Thermo-stimulated photo-ionization (delocalization) of electrons from the lowest field component of the 5d excited state of Ce³⁺ was observed in the Ce³⁺ singly doped sample under excitation at 355 nm. The 5d sublevel was found to locate at 0.3 eV below the conduction band of the host. However, the thermo-stimulated photo-ionization was greatly quenched due to the fast energy transfer from the 5d sublevel to Tb³⁺ ions in the Ce³⁺/Tb³⁺ double doped sample.     

Photoluminescence properties of rare earth doped α-Si3N4

The photoluminescence properties of Eu²⁺, Ce³⁺ and Tb³⁺ doped α-Si₃N₄ have been studied and a possible structural model has been proposed on the basis of the Rietveld refinement of X-ray powder diffraction data. Nearly single phase rare earth doped α-Si₃N₄ was synthesized by a solid state reaction at 1600 °C in N₂-H₂ atmosphere starting from amorphous Si₃N₄ and rare earth oxides or nitrides. Because of small crystal field splitting of the 5d levels, the excitation and emission bands of Eu²⁺ and Ce³⁺ are positioned at higher energies as isolated ions in comparison with that in Ca-α-Sialon. Both Eu²⁺- and Ce³⁺-doped α-Si₃N₄ show blue band emission peaking at about 470 and 450 nm, respectively, under UV excitation. α-Si₃N₄:Tb³⁺ exhibits dominant green line emission mainly arising from ⁵D₄→⁷F_J (J=6-3) with weak ⁵D₃→⁷F_J (J=6-3) transitions of Tb³⁺ when excited by UV light. The thermal stability of α-Si₃N₄:Eu²⁺ is comparable with that of Ca-α-Sialon:Eu²⁺ and is much better than that of α-Si₃N₄:Ce³⁺.     

Green emission from Tb-doped SrSi2O2N2 phosphors under ultraviolet light irradiation

Tb-doped SrSi₂O₂N₂ phosphors with promising luminescent properties were synthesized by the conventional solid-state reaction method, characterized by powder X-ray diffraction and studied by photoluminescence excitation and emission spectra. The synthesized materials exhibited a weak blue emission and a strong green emission in the region of 400-470 nm and 480-650 nm, which are attributed to ⁵D₃→⁷F_j (j=5, 4, 3) and ⁵D₄→⁷F_j (j=6, 5, 4, 3) transitions of Tb³⁺, respectively. The green emission from ⁵D₄→⁷F₅ at 543 nm showed the highest intensity under the optimized concentration of 0.1 mol, after which the quenching concentration became relevant. The quenching behavior of the emission of Tb³⁺ was explained by the cross-relaxation of its excited state.     

Fluorescent properties of a blue-to green-emitting Ce3+, Tb3+ codoped amorphous calcium silicate phosphors

Ce³⁺, Tb³⁺ codoped amorphous calcium silicate phosphor was prepared by heating (830 °C for 30 min) Ce³⁺, Tb³⁺ codoped calcium silicate hydrate phosphor formed by liquid-phase reaction. The excitation peak wavelength of the resulting phosphor was 330 nm and the emission peak wavelengths were at 544 nm, attributed to the ⁵D₄→⁷F₅ transition of Tb³⁺, and at 430–470 mm, attributed to Ce³⁺. The intensity ratio of the two peaks could be freely controlled by varying the Tb/Ca atomic ratio of the Ce³⁺, Tb³⁺ codoped amorphous calcium silicate phosphor, allowing light to be emitted over a wide range from blue to green. It was clarified that energy transfer exists from Ce³⁺ to Tb³⁺.     

A novel green phosphor GdCaAlO4:Tb for PDP application

A novel green-emitting nano-sized phosphor, Tb³⁺-doped GdCaAlO₄ was synthesized with a precursor prepared by citrate sol-gel method at relatively low temperature. Powder X-ray diffraction (XRD) analysis confirmed the formation of GdCaAlO₄. Field-emission scanning electron microscopy (FE-SEM) observation indicated a narrow size-distribution of about ∼100 nm for the particles with a spherical shape. Upon excitation with near UV and vacuum ultraviolet (VUV) light, the phosphor showed strong green-emission peaked at around 546 nm, corresponding to the ⁵D₄→⁷F₅ transition of Tb³⁺, and the highest photoluminescence (PL) intensity at 546 nm was found at a content of about 12 mol% Tb³⁺. As the Tb³⁺ concentration increases, the fast diffusion of energy among terbium ions toward traps or impurities resulting in a decrease of the lifetime. The optical properties study suggests that it is a potential candidate for plasma display panels (PDPs) application.     

Role of Yb and Tm ions in upconversion emission of Tb under 798 and 980 nm laser excitations in Tb-Tm-Yb doped tellurite glass

Upconversion emission and energy transfer processes in singly, doubly and triply doped tellurite glasses have been studied under 798 and 980 nm laser excitations. Emissions have been observed at 482, 544, 584, 655 nm and at 477, 655, 698, 800 nm corresponding to Tb³⁺: ⁵D₄ → ⁷F₆, ⁷F₅, ⁷F₄, ⁷F_J (J = 0, 1, 2, 3) and Tm³⁺: ¹G₄ → ³H₆, ¹G₄ → ³F₄, ³F₃ → ³H₆, ³H₄ → ³H₆ transitions, respectively. Among Tm³⁺, Yb³⁺and Tb³⁺ ions only Tm³⁺ has a ground state absorption at 798 nm excitation due to ³H₄ ← ³H₆ transition. For 980 nm excitation only Yb³⁺ can absorb the incident radiation. However, for both types of excitations, emission from all the three ions Tb, Yb and Tm has been observed. Possible mechanisms are proposed as follows: under 798 nm excitation Tm³⁺ ions are excited which excite Yb³⁺ ions through energy transfer. Finally “cooperative energy transfer” from a pair of Yb³⁺ ions to Tm³⁺ and Tb³⁺ ions takes place. Under 980 nm excitation Yb³⁺ ions absorb the incident energy and excite Tm³⁺ and Tb³⁺ ions via cooperative energy transfer. Variation of emission intensity with the ion concentrations of Yb³⁺, Tm³⁺ and Tb³⁺ has been studied. The lifetime of the ¹G₄ level has also been measured.     

VUV spectroscopic properties of Ce and Pr-doped AREP2O7-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu)

Spectroscopic properties of Ce³⁺ and Pr³⁺-doped AREP₂O₇-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu) have been investigated using VUV spectroscopy technique. Ce³⁺-doped samples show typical Ce³⁺ emission in the range of 325-450 nm. The strong host absorption band starting at around 160 nm indicates that the optical band gap of AREP₂O₇ hosts is at least 7.7 eV, and the host→Ce³⁺ energy transfer process is rather efficient. However, AREP₂O₇:Pr³⁺ samples show less efficient host→Pr³⁺ energy transfer. The direct Pr³⁺ 4f²→4f¹5d¹ excitation, which are 12160±640 cm⁻¹ higher respect to that of Ce³⁺, leads to strong 4f¹5d¹→4f² emission bands in the range of 230-325 nm but no obvious 4f²→4f² emission lines.     

The effect of codopants on spectral-kinetic characteristics of luminescence of scintillation glasses doped with terbium ions

The effect of Ce³⁺ and Pr³⁺ ions on spectral-kinetic characteristics of luminescence of lithium–phosphate–borate glasses is studied. It is shown that terbium ion luminescence caused by transitions from ⁵D₃ and ⁵D₄ multiplets to the ground 7FJ term is detected in samples containing Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺. It has been found that an increase in the concentration of cerium ions from 0.2 to 1 wt % leads to an increase in the intensity of main luminescence bands of terbium ions. In Tb³⁺/Pr³⁺ glasses, a decrease in the relative light yield is observed with an increase in the concentration of Pr³⁺ ions. Processes of energy transfer between Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺ ions are discussed.     

Luminescence enhancement by energy transfer from Ce ions in Ba1.6Ca0.4P2O7:Ce:Tb phosphor

The optical properties of Ba_1.6Ca_0.4P₂O₇ doped with Ce³⁺ and Tb³⁺ are investigated. Under excitation at 280 nm the emission spectrum of Ba_1.6Ca_0.4P₂O₇:Ce³⁺ consists of a peak at 370 nm and a shoulder at the longer wavelength side. The emission spectra of Ba_1.6Ca_0.4P₂O₇:Tb³⁺ shows the well-known emission lines due to ⁵D₄-⁷F_J transitions of Tb³⁺. The green emissions of Tb³⁺ ions are enhanced upon UV excitation through energy transfer from Ce³⁺ to Tb³⁺ ions. The efficiency of such an energy transfer is estimated based on spectroscopic data. The dependence of photoluminescence (PL) intensities of Ce³⁺ and Tb³⁺ emissions on Ce³⁺ or Tb³⁺ concentrations in the systems (Ba_1.6Ca_0.4P₂O₇:0.04Ce³⁺,xTb³⁺ and Ba_1.6Ca_0.4P₂O₇:xCe³⁺,0.04Tb³⁺) and the temperature dependence of PL emission spectra of Ba_1.6Ca_0.4P₂O₇:0.06Ce³⁺,0.04Tb³⁺ is also investigated.     

Enhanced luminescent properties and optical absorption of γ-irradiated KI: Ce, Tb crystals

This paper reports that KI doped with Ce³⁺ or double doped with Tb³⁺ and Ce³⁺ were prepared by the Bridgman-Stockbarger method and characterized by optical absorption photoluminescence (PL), thermoluminescence (TL), photostimulated emission (PSL) and TL emission. The optical absorption measurement indicates that F and V₁, V₂ centers are formed in the crystals during the γ irradiation process. It was attempted to incorporate a broad band of Ce³⁺ activator into the narrow band emission of Tb³⁺ in the KI host without the reduction of emission intensity. Ce³⁺-co-doped KI and Tb crystals showed a broad band emission due to the d-f transition of Ce³⁺ and a reduction in the intensity of emission peaks due to the ⁵D₃-⁷F_j (j=3,4,5,6) transition of Tb³⁺, when they were excited at 240 nm.These results supported that an effective energy transfer occurs from Tb³⁺ to Ce³⁺ in the KI host. Co-doping Ce³⁺ ions greatly intensified the excitation peak at 260 nm for the emission at 393 nm of Tb³⁺, which means that more lattice defects, involved in the energy absorption and transfer to Tb³⁺, are formed by the Ce³⁺ co-doping. The integrated light intensity is an order of magnitude higher as compared to the undoped samples for similar doses of irradiation and heating rates. The defects generated by irradiation were monitored by optical absorption and TSL Trap parameters for the TL process are calculated and presented.