Luminescent properties and energy transfer of Y3Al5O12:Ce3+, Ln3+ (Ln=Tb,Pr) prepared by polymer-assisted sol–gel method

Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and Y₃Al₅O₁₂:Ce³⁺, Tb³⁺ nano-particles have been synthesized by polymer-assisted sol–gel method. Crystal structure, luminescent properties and energy transfer of the phosphors are analyzed. XRD study of polycrystalline powders shows that all the samples are of YAG phase without impurity. Photoluminescence (PL) emission and excitation spectra illustrate that in YAG:Ce, Pr phosphors, energy transfer occurs mutually between Ce³⁺ and Pr³⁺, while in YAG:Ce, Tb systems, only one-way path energy transfer of Tb³⁺→Ce³⁺ is observed.     

Energy transfer in Y3Al5O12:Ce, Pr and CaMoO4:Sm, Eu phosphors

Non-radiative energy transfers (ET) from Ce³⁺ to Pr³⁺ in Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and from Sm³⁺ to Eu³⁺ in CaMoO₄:Sm³⁺, Eu³⁺ are studied based on photoluminescence spectroscopy and fluorescence decay patterns. The result indicates an electric dipole-dipole interaction that governs ET in the LED phosphors. For Ce³⁺ concentration of 0.01 in YAG:Ce³⁺, Pr³⁺, the rate constant and critical distance are evaluated to be 4.5×10⁻³⁶ cm⁶ s⁻¹ and 0.81 nm, respectively. An increase in the red emission line of Pr³⁺ relative to the yellow emission band of Ce³⁺, on increasing Ce³⁺ concentration is observed. This behavior is attributed to the increase of spectral overlap integrals between Ce³⁺ emission and Pr³⁺ excitation due to the fact that the yellow band shifts to the red spectral side with increasing Ce³⁺ concentration. In CaMoO₄:Sm³⁺, Eu³⁺, Sm³⁺-Eu³⁺ transfer occurs from ⁴G_5/2 of Sm³⁺ to ⁵D₀ of Eu³⁺. The rate constant of 8.5×10⁻⁴⁰ cm⁶ s⁻¹ and the critical transfer distance of 0.89 nm are evaluated.     

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.     

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.     

Luminescence properties and energy transfer in Ba2Y(BO3)2Cl:Ce3+,Tb3+ phosphors

Novel green-emitting Ba₂Y(BO₃)₂Cl:Ce³⁺,Tb³⁺ phosphors were synthesized by a solid-state method. X-ray diffraction and photoluminescence spectra were utilized to characterize the structures and luminescence properties of the as-synthesized phosphors, respectively. Ba₂Y(BO₃)₂Cl:Ce³⁺,Tb³⁺ phosphors exhibit blue and green emission bands under the excitation of near-ultraviolet light. An asymmetric blue emission originates from the Ce³⁺ ion, whereas the green emission originates from the Tb³⁺ ion. A spectral overlap is found between the emission band of the Ce³⁺ ion and the excitation band of the Tb³⁺ ion, which supports the occurrence of the energy transfer from the Ce³⁺ ion to the Tb³⁺ ion. Meanwhile, the energy transfer is thoroughly investigated by their photoluminescence decay behaviors. The energy-transfer efficiency from the Ce³⁺ ion to the Tb³⁺ ion is also calculated, and a possible mechanism is proposed.     

Luminescence studies on lanthanide ions (Eu, Dy and Tb) doped YAG:Ce nano-phosphors

Yttrium aluminum garnet nanoparticles both undoped and doped with lanthanide ions (Ce³⁺, Eu³⁺, Dy³⁺ and Tb³⁺) having average size around 30 (±3 nm) nm were prepared by glycine nitrate combustion method followed by annealing at a relatively low temperature of 800 °C. Increase in the annealing temperature has been found to improve the luminescence intensity and for 1200 °C heated samples there exists strong energy transfer from Tb³⁺ to Ce³⁺ ions in YAG:Ce(2%),Tb(2%) nanoparticles as revealed by luminescence studies. Co-doping the YAG:Ce nanoparticles with Eu³⁺ results in significant decrease in the emission intensity of both Ce³⁺ and Eu³⁺ ions and this has been attributed to the oxidation of Ce³⁺ to Ce⁴⁺ and reduction of Eu³⁺ to Eu²⁺ ions. Dy³⁺ co-doping did not have any effect on the Ce³⁺ emission as there is no energy transfer between Dy³⁺ and Ce³⁺ ions.     

Luminescence properties of CaS:Ce, Sm nanophosphors

CaS:Ce, Sm nanophosphors were synthesized via solid state diffusion method. X-Ray diffraction confirmed the cubic crystalline phase of CaS:Ce, Sm nanoparticles. The particle size calculated using Debye-Scherrer formula was found to be 52 nm. The morphological investigations of the nanoparticles were made using TEM and found to have nearly spherical morphology with diameter 45-50 nm, which is in close agreement with the XRD result. The PL emission characteristics of CaS:Ce, Sm as a function of cerium and samarium concentrations have been studied and CaS:Ce_0.6Sm_0.4 system has maximum emission intensity, hence it was opted for further studies. The CaS:Ce_0.6Sm_0.4 system showed independent emission of Sm and Ce when excited at 330 and 450 nm, respectively. To study the energy transfer between cerium and samarium, the CaS:Ce_0.6Sm_0.4 was excited at wavelengths other than the excitation wavelengths of Ce (450 nm) and Sm (330 nm). The existence of Ce emission (at an excitation of 390 nm) even in the absence of Ce excitation band and Sm emission at an excitation of 405 nm, which is the excitation band of Ce, indicates the energy transfer at these two wavelengths. Thermoluminescence characteristics of ⁶⁰Co irradiated CaS:Ce_0.6Sm_0.4 have been investigated for different doses of 0.14-125 Gy. All the glow curves show a single peak at 475 K. With increasing dose, the intensity of this peak increases and a shoulder is formed on the lower temperature side at 415 K at 21 Gy of exposure. CaS:Ce_0.6Sm_0.4 shows almost linear dose dependence up to 125 Gy.     

Luminescence and Tb-Ce-Eu ion energy transfer in single-crystalline films of Tb3Al5O12:Ce,Eu garnet

The paper is devoted to investigation of the processes of excitation energy transfer between the host cations (Tb³⁺ ions) and the activators (Ce³⁺ and Eu³⁺ ions) in single-crystalline films of Tb₃Al₅O₁₂:Ce,Eu (TbAG:Ce,Eu) garnet which is considered as a promising luminescent material for the conversion of LED's radiation. The cascade process of excitation energy transfer is shown to be realized in TbAG:Ce,Eu: (i) from Tb³⁺ ions to Ce³⁺ and Eu³⁺ ions; (ii) from Ce³⁺ ions to Eu³⁺ ions by means of dipole-dipole interaction and through Tb³⁺ ion sublattice.     

Preparation,luminescence and structural properties of rare‐earth‐doped RbLuS2 compounds

Rare‐earth (RE = Ce, Pr, Sm, Tb) doped ternary sulfides of the general formula RbLu_0.99RE_0.01S₂ and undoped RbLuS₂ were synthesized in the form of crystalline hexagonal platelets by chemical reaction in the electric resistance furnace under the flow of hydrogen sulfide. Only a single crystalline phase of the rhombohedral lattice system (space group $ {\rm R}\bar 3{\rm m}) $ was detected by X‐ray powder diffraction. Absorption and luminescence characteristics were measured. The band edge of RbLuS₂ is found at 310 nm, and characteristic Pr³⁺, Sm³⁺ and Tb³⁺ 4f–4f emission lines in the visible spectral range are observed. A charge transfer transition in the Pr³⁺ excitation spectrum in the near UV spectral region is revealed and an efficient energy transfer from the host to the emission centers is found. The application potential for white LED or X‐ray phosphors is discussed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Luminescence properties and energy transfer investigations of BaAl2B2O7:Ce3+,Tb3+ phosphors

Ce³⁺ and Tb³⁺ co-doped BaAl₂B₂O₇ phosphors were synthesized by the solid-state method. X-ray diffraction (XRD) was used to characterize the phase structure. The photoluminescent properties of Ce³⁺ and Tb³⁺ co-doped BaAl₂B₂O₇ phosphors were investigated by using the photoluminescence emission and excitation spectra. Under the excitation of near ultraviolet (n-UV) light, BaAl₂B₂O₇:Ce³⁺,Tb³⁺ phosphors exhibited blue emission corresponding to the f–d transition of Ce³⁺ ions and green emission bands corresponding to the f–f transition of Tb³⁺ ions, respectively. Effective energy transfer occurred from Ce³⁺ to Tb³⁺ in BaAl₂B₂O₇ host due to the observed spectra overlap between the emission spectrum of Ce³⁺ ion and the excitation spectrum of Tb³⁺ ion. The energy transfer efficiency from Ce³⁺ ion to Tb³⁺ ion was also calculated to be 71%. Furthermore, the concentration quenching and critical distance of BaAl₂B₂O₇:Ce³⁺,Tb³⁺ phosphors were also discussed. The energy transfer from Ce³⁺ to Tb³⁺ in BaAl₂B₂O₇ host was demonstrated to be resonant type via a dipole–dipole interaction mechanism with the energy transfer critical distance of 16.13 Å.     

Spectroscopy and energy level location of the trivalent lanthanides in LiYP4O12

The excitation and emission properties of the lanthanides Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Tb³⁺, Er³⁺, Tm³⁺, and Yb³⁺ in LiYP₄O₁₂ were studied by vacuum ultra-violet spectroscopy at 10 K. It provides information on the energies of 4f-5d excitation and emission bands. In the case of Er³⁺ spin forbidden emission was observed. Charge transfer excitation bands were identified for Eu³⁺, Sm³⁺, Tm³⁺, and Yb³⁺, and in the case of Yb³⁺ charge transfer luminescence is observed. All data appear to be consistent with each other and have been used to construct a level scheme showing the location of the energy levels of all trivalent and divalent lanthanides in LiYP₄O₁₂.     

Luminescence properties of phosphors based on Tb<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> (TbAG) terbium-aluminum garnet

The processes of excitation energy transfer in phosphors based on single-crystal Tb₃Al₅O₁₂:Ce (TbAG:Ce) and Tb₃Al₅O₁₂:Ce,Eu (TbAG:Ce,Eu) garnet films have been investigated. These films are considered to be promising materials for screens for X-ray images and luminescence converters of blue LED radiation. The conditions for excitation energy transfer from the matrix (Tb³⁺ cations) to Ce³⁺ and Eu³⁺ ions in TbAG:Ce and TbAG:Ce,Eu phosphors have been analyzed in detail. It is established that a cascade process of excitation energy transfer from Tb³⁺ ions to Ce³⁺ and Eu³⁺ ions and from Ce³⁺ ions to Eu³⁺ ions is implemented in TbAG:Ce,Eu via dipole-dipole interaction and through the Tb³⁺ cation sublattice.     

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⁺.     

The energy transfer mechanism in Ce,Tb co-doped LaF3 nanoparticles

LaF₃ pure host, LaF₃:Ce, LaF₃:Tb as well as LaF₃:Ce,Tb phosphors were synthesized by the hydrothermal method. X-ray diffraction measurements were in good agreement with the standard data of LaF₃ from JCPDS card No. 32-0483 and indicated that the material was nanocrystalline with an average particle size of about 36 nm. Photoluminescence spectra of co-doped samples revealed that the Ce³⁺ emission was quenched while Tb³⁺ emission was enhanced, implying that energy was transferred from Ce³⁺ (the donor) to Tb³⁺ (the acceptor) in this system. The luminescence intensities and lifetimes of the donor for different concentrations of the acceptor were fitted to theoretical models in order to investigate the energy transfer mechanism. The quadrupole–quadrupole and exchange interaction mechanisms gave the best fit between the experimental data and the theoretical curves. The effective average Bohr radius from the fit to the exchange model is 0.095 nm. Since this is close to the ionic radii of the Ce³⁺ and Tb³⁺ ions, it suggests that the exchange interaction mechanism contributes to the energy transfer.     

KBaPO4:Ln (Ln=Eu, Tb, Sm) phosphors for UV excitable white light-emitting diodes

This letter reports the novel three emission bands based on phosphate host matrix, KBaPO₄ doped with Eu²⁺, Tb³⁺, and Sm³⁺ for white light-emitting diodes (LEDs). The phosphors were synthesized by solid-state reaction and thermal stability was elucidated by measuring photoluminescence at higher temperatures. Eu²⁺-doped KBaPO₄ phosphor emits blue luminescence with a peak wavelength at 420 nm under maximum near-ultraviolet excitation of 360 nm. Tb³⁺-doped KBaPO₄ phosphor emits green luminescence with a peak wavelength at 540 nm under maximum near-ultraviolet excitation of 370 nm. Sm³⁺-doped KBaPO₄ phosphor emits orange-red luminescence with a peak wavelength at 594 nm under maximum near-ultraviolet excitation of 400 nm. The thermal stabilities of KBaPO₄:Ln (Ln=Eu²⁺, Tb³⁺, Sm³⁺), in comparison to commercially available YAG:Ce³⁺ phosphor were found to be higher in a wide temperature range of 25-300 °C.     

Cerium and terbium luminescence in LaMgAl11O19

Under 254 nm excitation LaMgAl₁₁O₁₉ : Ce³⁺ shows emission peaking between 340 and 360 nm with a quantum efficiency up to 65%, which is almost independent of the Ce³⁺ concentration. Energy transfer between the Ce³⁺ ions is not efficient. In CeMgAl₁₁O₁₉ : Tb³⁺ efficient energy transfer occurs from Ce³⁺ to Tb³⁺, resulting in a green emission with a quantum efficiency up to 65%. The Ce³⁺ - Tb³⁺ energy transfer is ascribed to electric dipole-quadrupole interaction.     

Green light emission by Ce3+ and Tb3+ co-doped Sr3MgSi2O8 phosphors for potential application in ultraviolet whitelight-emitting diodes

Sr₃MgSi₂O₈:Ce³⁺, Tb³⁺ phosphor samples were prepared using a solid-state reaction technique, and the photoluminescence properties and energy transfer were investigated. Effective energy transfer occurred in Ce³⁺/Tb³⁺ co-doped Sr₃MgSi₂O₈ phosphors. Co-doping of Ce³⁺ was found to enhance the emission intensity of Tb³⁺ to a certain extent by transferring energy to Tb³⁺. The Ce³⁺/Tb³⁺ energy transfer was thoroughly investigated through its emission/excitation spectra and photoluminescence decay behavior. The color emitted by Sr₃MgSi₂O₈:Ce³⁺, Tb³⁺ phosphors varied from blue to green and can be controlled by altering the concentration ratio of Ce³⁺ to Tb³⁺. These results indicate that Sr₃MgSi₂O₈:Ce³⁺, Tb³⁺ may be useful as a green-emitting phosphor for ultraviolet whitelight-emitting diodes.     

Spectral investigation of R,Ce:YAG(R: Pr~(3+), Eu~(3+), Gd~(3+)) single crystals and their applications in white LEDs

Eu3+, Pr3+, or Gd3+codoped Ce:YAG single crystals were grown by using the Czochralski method. The photoluminescence(PL) emission and excitation spectra and transmittance were measured and investigated. The additional red-emitting bands were observed in the PL emission spectra of Eu,Ce:YAG and Pr,Ce:YAG single crystals and the formation of noticeable peaks was studied with reference to the schematic energy level diagrams. A red-shifted phenomenon was observed in the PL emission spectrum of Gd,Ce:YAG. With codoped Eu3+, Pr3+, or Gd3+ions, warmer white light was achieved for the white light emitting diodes and the color rendering index became higher.     

The effect of Ce3+ ions on the spectral and decay characteristics of luminescence phosphate-borate glasses doped with rare-earth ions

The luminescent characteristics of Li₂O-B₂O₃-P₂O₅-CaF₂ (LBPC) glasses doped with Gd³⁺ and Tb³⁺ ions and codoped with Ce³⁺ are studied by pulsed optical spectrometry under electron beam excitation. It is found that in glass with Ce³⁺ and Gd³⁺ ions a decrease in the decay time of gadolinium luminescence in the 312-nm band (⁶ P _J → ⁸ S _7/2) was observed. It is shown that in the glass LBPC: Tb, Ce, an increase in the emission intensity in the main radiative transitions in terbium ion was observed. In the kinetics of luminescence band 545 nm of LBPC: Tb, Ce glasses, is present stage of buildup, the character of which changes with the doped of Ce³⁺ ions. The mechanism of energy transfer in LBP glasses doped with rare elements is discussed.