Energy transfer processes in Ce and Tb co-doped Ln2Si2O7 (Ln = Y, Gd)

The Ce³⁺ and Tb³⁺ co-doped Ln₂Si₂O₇ (Ln = Y, Gd) samples were prepared by sol-gel method. Structure characterization of the phosphor was carried out by X-ray diffraction. The luminescence properties of samples were analyzed by measuring the excitation and emission spectra. It was observed that excitation energy can transfer mutually between Ce³⁺ and Tb³⁺ in GPS: Ce³⁺, Tb³⁺ samples, while in Y₂Si₂O₇ :Ce³⁺, Tb³⁺ samples the energy transfer only progresses from Ce³⁺ to Tb³⁺. Based on the energy level diagrams of respective Ce³⁺, Tb³⁺ and Gd³⁺ ion, the detailed pathways for energy transfer are explained.     

Co-existence phenomenon of Ce3+/Ce4+ and Tb3+ in Ce/Tb co-doped Zn2(BO3)(OH)0.75F0.25 phosphor: Luminescence and energy transfer

A serials of Zn₂(BO₃)(OH)_0.75F_0.25 (ZBF), Tb³⁺, Ce^3+/4+ single-doped ZBF and Tb³⁺/Ce^3+/4+ co-doped ZBF novel phosphors with belt-like morphology were obtained through hydrothermal reaction without any surfactant. The obtained samples were characterized by XRD, SEM, EDS, TEM, TGA, XPS, DR, PL, and DT. The TGA curve shows that the phosphor is thermal stability. XPS results show that Tb³⁺ is present in the Tb-doped phosphor, and the Ce³⁺/Ce⁴⁺ mixed valence is present in the Ce-doped phosphor. The PL results indicate that ZBF host material and ZBH:Ce^3+/4+ can emit blue light, ZBF:Tb³⁺ can emit green light. Compared with the Tb³⁺ single doped phosphor, the Tb³⁺/Ce^3+/4+ co-doped phosphors shown stronger emission and shorter decay time, which is attributed to the effective energy transfer from the Ce^3+/4+ to Tb³⁺ ions.     

Luminescence properties and energy transfer of a novel bluish-green tunable NaBa4(BO3)3:Ce3+, Tb3+ phosphor

A series of single-phased emission tunable NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ phosphors were synthesized by solid-state reaction. The crystal structure, photoluminescence properties, concentration quenching and energy transfer of NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ were systematically investigated. The wavelength-tunable bluish-green light can be realized by coupling the emission bands centered at 425 and 543 nm ascribed to the contribution from Ce³⁺ and Tb³⁺, respectively. The energy transfer from Ce³⁺ to Tb³⁺ in NaBa₄(BO₃)₃ host was studied and demonstrated to be a resonant type via a dipole–dipole interaction mechanism. The energy transfer efficiency (Ce³⁺ → Tb³⁺) obtained by decay curves was consistent with the result calculated by the emission intensity, which gradually increased from 0% to 84.5% by increasing the Tb³⁺ doping content from 0 to 0.45. The results indicate that the NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ phosphors have potential applications as an ultraviolet-convertible phosphor due to its effective excitation in the ultraviolet rang.     

Structural and optical characterization of RE (Eu<Superscript>2+</Superscript>, Ce<Superscript>3+</Superscript>) doped SrMg<Subscript>2</Subscript>Al<Subscript>6</Subscript>Si<Subscript>9</Subscript>O<Subscript>30</Subscript> nanocrystalline phosphor

This article present the reports on optical study of Eu²⁺ and Ce³⁺ doped SrMg₂Al₆Si₉O₃₀ phosphors, which has been synthesized by combustion method at 550 °C. Here SrMg₂Al₆Si₉O₃₀:Eu²⁺ emission band observed at 425 nm by keeping the excitation wavelength constant at 342 nm, whereas SrMg₂Al₆Si₉O₃₀:Ce³⁺ ions shows the broad emission band at 383 nm, under 321 nm excitation wavelength, both the emission bands are assigned due to 5d–4f transition respectively. Further, phase purity, morphology and crystallite size are confirmed by XRD, SEM and TEM analysis. However, the TGA analysis is carried out to know the amount of weight lost during the thermal processing. The CIE coordinates of SrMg₂Al₆Si₉O₃₀:Eu²⁺ phosphor is observed at x?=?0.160, y?=?0.102 respectively, which may be used as a blue component for NUV-WLEDs. The critical distance of energy transfer between Ce³⁺ ions and host lattice is found to be 10.65 Å.     

Luminescence and structural properties of Eu3+ doped BaY2ZnO5 for LED solid-state lighting application

Eu³⁺ doped BaY_2(1?x)ZnO₅ phosphor was successfully synthesized by a single step solution combustion process. The crystal structure and particle morphology were investigated by X-ray diffraction (XRD), scanning electron microscopy and transmission electron microscopy. The XRD results suggest that BaY₂ZnO₅ crystallizes in a single phased orthorhombic structure with space group Pbnm at 1,100 °C. The phosphor can be effectively excited by near-UV light, emitting intense red luminescence (628 nm) corresponding to the hypersensitive ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions, located at low-symmetry site with no inversion center in BaY₂ZnO₅ crystal lattice. Fluorescence decay analysis was carried out to understand the energy transfer mechanism and quenching behavior of luminescence of Eu³⁺ ions in the BaY₂ZnO₅ phosphor. The BaY₂ZnO₅: Eu³⁺ emission (λ_ex = 395 nm) could be tuned from blue to white and red light by varying the Eu³⁺ ions concentration, making this phosphor as a promising candidate for LEDs application.     

Luminescence properties and energy transfer studies of a color tunable BaY2Si3O10:Tm3+,Dy3+ phosphor

A series of color-tunable and white light emitting phosphors BaY₂Si₃O₁₀:Tm³⁺,Dy³⁺ were synthesized by a high temperature solid-state reaction, and their phase structure, photoluminescence properties, and energy transfer processes between rare-earth ions were investigated in detail. Upon UV excitation, white light emission depending on dopant concentrations could be achieved by integrating a blue emission band located at 458 nm and an orange one located at 576 nm attributed to Tm³⁺ and Dy³⁺ ions, respectively. In addition, the energy transfer process between Tm³⁺ and Dy³⁺ ions was demonstrated to be a resonant type via a dipole–quadrupole mechanism. Preliminary studies showed that the phosphor might be promising as a single-phased white-light-emitting phosphor for UV chip pumped white-light LEDs.     

Luminescence properties and energy transfer of co-doped Ba<Subscript>3</Subscript>GdNa(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>F:Ce<Superscript>3+</Superscript>,Tb<Superscript>3+</Superscript> green-emitting phosphors

Phase pure Ce³⁺ and Tb³⁺ singly doped and Ce³⁺/Tb³⁺ co-doped Ba₃GdNa(PO₄)₃F samples have been synthesized via the high temperature solid-state reaction. The crystal structures, photoluminescence properties, fluorescence lifetimes, thermal properties and energy transfer of Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ were systematically investigated. Rietveld structure refinement indicates that Ba₃GdNa(PO₄)₃F crystallizes in a hexagonal crystal system with the space group P-6. For the co-doped Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ samples, the emission color can be tuned from blue to green by varying the doping concentration of the Tb³⁺ ions. The intense green emission was realized in the Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ phosphors on the basis of the highly efficient energy transfer from Ce³⁺ to Tb³⁺. Also the energy transfer mechanism has been confirmed to be quadrupole–quadrupole interaction, which can be validated via the agreement of critical distances obtained from the concentration quenching (13.84 Å). These results show that the developed phosphors may possess potential applications in near-ultraviolet pumped white light-emitting diodes.     

Structural and luminescence study of Ce3+ and Tb3+ doped Ca3Sc2Si3O12 garnets obtained by freeze-drying synthesis method

Ca₃Sc₂Si₃O₁₂ garnets doped with Ce³⁺ and Tb³⁺ ions were synthesized by a freeze-drying precursor method. The structural characterization was performed by X-ray diffraction (XRD) and Raman spectroscopy. Scanning Electron Microscopy (SEM) images of the calcined material were studied. High temperature treatments and doping with RE³⁺ ions resulted in a reduction of the secondary phases (Sc₂O₃) and an increase of the mean size of the nanocrystals, from 75 to 149 nm. These effects were confirmed by means of Raman spectra. Moreover, luminescence features of Ce³⁺ and Tb³⁺ doped samples indicated that these ions are effectively incorporated into the crystalline phase. In addition, the energy transfer processes between Ce³⁺ and Tb³⁺ ions in codoped garnets have been studied.     

Ce to Tb energy transfer in alkaline earth (Ba, Sr or Ca) sulphate phosphors

Energy transfer between Ce³⁺ and Tb³⁺ dopants in alkaline earth (Ba, Sr or Ca) sulphate phosphors is investigated. Among these three phosphors, CaSO₄:Ce³⁺,Tb³⁺ showed maximum Tb³⁺ green emission on excitation with UV light. Photoluminescence measurements reveal that the emission intensity from CaSO₄:Ce³⁺,Tb³⁺ is comparable with that of the commercial green lamp phosphor Ce_0.65Tb_0.35MgAl₁₁O₁₉. Optimum concentrations of dopants in CaSO₄:Ce³⁺,Tb³⁺ are 0.2 mol% each and the optimum sintering treatment following re-crystallisation is 600 °C for 1 h duration. The effect of charge compensator in all the three phosphors is also studied.     

Synthesis and luminescence of BiPO4:Ln3+ (Ln = Ce3+, Tb3+) phosphors

BiPO₄:Ce³⁺ and BiPO₄:(Ce³⁺, Tb³⁺) powders were synthesized by the method of precipitation. The X-ray diffraction patterns show that BiPO₄:Ce³⁺ and BiPO₄:(Ce³⁺, Tb³⁺) samples have pure hexagonal phases. The transmission electron microscopy results show that the synthesized samples are nanoparticles. Ethylene glycol plays an important role in the formation of nanoparticles. The excitation spectrum of BiPO₄:Ce³⁺ sample shows the transition from the ground ² F _5/2 state to the excited 5d states of the Ce³⁺ ions. The emission spectrum exhibits a strong band centered at 352 nm originating from the 5d → 4f transitions of the Ce³⁺ ions. The emission spectrum of the BiPO₄:(Ce³⁺, Tb³⁺) sample contains both a weak emission band of the Ce³⁺ ions and strong green emission bands of the Tb³⁺ ions. The excitation and emission spectra show that there are energy transfers between Ce³⁺ and Tb³⁺ ions in the BiPO₄:(Ce³⁺, Tb³⁺) sample. The energy transfers between Ce³⁺ and Tb³⁺ ions improve the emission efficiency of BiPO₄:(Ce³⁺, Tb³⁺) sample.     

Synthesis,crystal structure and luminescence in Ca<Subscript>3</Subscript>Al<Subscript>2</Subscript>O<Subscript>6</Subscript>

Bluish green emitting phosphor, Ca₃Al₂O₆:Ce³⁺, is prepared by low-temperature combustion method. X-ray diffraction, photoluminescence, scanning electron microscopy techniques are used to characterize the synthesized phosphor. The most efficient bluish green (483 nm) emission is observed under the excitation by near UV light. The emission characteristics are credited to 5d → 4f type transitions in Ce³⁺. The luminescence properties of Eu²⁺ are predicted for the first time from those of Ce³⁺. Also, photoluminescence of Eu³⁺ is studied in the same host. The emission spectrum of Ca₃Al₂O₆:Eu³⁺ shows the peak at 592 (orange) and 614 nm (red) wavelengths. Ca₃Al₂O₆:Ce³⁺phosphor can be a potential blue phosphor for field emission display, solid-state lighting and LED.     

Luminescence properties and preparation of Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> powder doped with Ce and Pr ions

Lu₃Al₅O₁₂:Ce³⁺ phosphor powder, which exhibits green emission band, was synthesized by the high-temperature solid-state reaction method with a flux BaF₂. X-ray diffraction (XRD), photoluminescence (PL) spectra, and fluorescent lifetime spectra were used to characterize the structure and luminescent properties of the sample. The XRD patterns indicated that when prepared at 1550 °C for 3 h with 4 wt% flux, Lu₃Al₅O₁₂:Ce³⁺ phosphors powder is the garnet cubic crystal system structure. Photoluminescence (PL) spectra showed that the Lu₃Al₅O₁₂:Ce³⁺ phosphor powder can be effectively excited by near ultraviolet and blue light, emitting broad band peaking at 505 nm, which is attributed to ²F_5/2?→?²D_5/2 transition. The self-concentration quenching mechanism of Ce³⁺ is the dipole–dipole interaction. Small amount of Pr³⁺ increased red light emission at 610 nm. Photoluminescence (PL) spectra and fluorescent lifetime spectra indicated that there was an efficient energy transfer process between Ce³⁺ and Pr³⁺.     

Long wavelength Ce emission in Y6Si3O9N4 phosphors for white-emitting diodes

Y₆Si₃O₉N₄:Ce³⁺ phosphor was prepared by a solid-state reaction in reductive atmosphere. X-ray powder diffraction (XRD) analysis confirmed the formation of Y₆Si₃O₉N₄:Ce³⁺. Scanning electron microscopy (SEM) observation indicated that the microstructure of the phosphor consisted of irregular fine grains with an average size of about 5 μm. Photoluminescence (PL) measurements showed that the phosphor can be efficiently excited by near ultraviolet (UV) or blue light excitation, and exhibited bright green emission peaked at about 525 nm. Compared with Ce³⁺-doped Y₄Si₂O₇N₂ phosphors, Ce³⁺-doped Y₆Si₃O₉N₄ phosphors showed longer wavelengths of both excitation and emission. The Y₆Si₃O₉N₄:Ce³⁺ is a potential green-emitting phosphor for white LEDs.     

White light generation in Al2O3:Ce:Tb:Mn films deposited by ultrasonic spray pyrolysis

Aluminium oxide (Al₂O₃) films doped with CeCl₃, TbCl₃ and MnCl₂ were deposited at 300 °C with the ultrasonic spray pyrolysis technique. The films were analysed using the X-ray diffraction technique and they exhibited a very broad band without any indication of crystallinity, typical of amorphous materials. Sensitization of Tb³⁺ and Mn²⁺ ions by Ce³⁺ ions gives rise to blue, green and red simultaneous emission when the film activated by such ions is excited with UV radiation. The overall efficiency of such energy transfer results to be about 85% upon excitation at 312 nm. Energy transfer from Ce³⁺ to Tb³⁺ ions through an electric dipole-quadrupole interaction mechanism appears to be more probable than the electric dipole-dipole one. A strong white light emission for the Al₂O₃:Ce³⁺(1.3 at.%):Tb³⁺(0.2 at.%):Mn²⁺(0.3 at.%) film under UV excitation is observed. The high efficiency of energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions, resulting in cold white light emission (x = 0.30 and y = 0.32 chromaticity coordinates) makes the Ce³⁺, Tb³⁺ and Mn²⁺ triply doped Al₂O₃ film an interesting material for the design of efficient UV pumped phosphors for white light generation.     

Synthesis and luminescence of Sr3Al2O6:Ce3+ powders synthesized by solid state reaction method with addition of H3BO3

Sr₃Al₂O₆:Ce³⁺ powders were synthesized using a solid state reaction method in air with addition of H₃BO₃. The effects of Ce³⁺ dopant concentrations and the weight ratio (wt) of H₃BO₃ to total raw materials weight on the formation of Sr₃Al₂O₆:Ce³⁺ samples were investigated. Single-phase and well-crystallized Sr₃Al₂O₆:Ce³⁺ samples can be obtained when the addition of H₃BO₃ is lower than 7 wt%. The excitation spectrum indicates that Sr₃Al₂O₆:Ce³⁺ phosphor powders exhibit two excitation bands centered at 345 and 462 nm. The emission spectrum shows that Sr₃Al₂O₆:Ce³⁺ phosphor powders exhibit an emission band peaked at 536 nm when excited at 462 nm. Sr₃Al₂O₆:Ce³⁺ sample at the Ce³⁺ concentration of 5 mol% shows the strongest emission intensity. The addition of H₃BO₃ has obvious influence on phase and emission intensity of Sr₃Al₂O₆:Ce³⁺ phosphors. The results show that the Sr_2.95Ce_0.05Al₂O₆ sample with the 7 wt% addition of H₃BO₃ has the highest emission intensity and the longest lifetime.     

The luminescence of bismuth and manganese in LaMgB5O10

The luminescences of Bi³⁺ and Mn²⁺ in LaMgB₅O₁₀ are reported. The emission of the Bi₃₊ ion shows a small Stokes shift and is situated in the ultraviolet. From the decay times the ³P₀ and ³P₁ levels appear to be mixed. At 4.2 K no energy transfer between Bi³⁺ ions occurs, but at room temperature the critical distance for this energy transfer amounts to some 25 Å. This knowledge is used to explain energy transfer between Bi³⁺ and Tb³⁺ in LaMgB₅O₁₀, which is compared with that between Ce³⁺ and Tb³⁺ in the same lattice. The Mn²⁺ ion shows a red emission in LaMgB₅O₁₀. The Bi₃₊ ion acts as a sensitizer for this emission, whereas the Ce³⁺ ion does not.     

Luminescent properties of single-phase Ba<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>:Tb<Superscript>3+</Superscript>, R (R = Eu<Superscript>2+</Superscript>, Ce<Superscript>3+</Superscript>) phosphors for white LED

The Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) phosphors were synthesized by use of a co-precipitation method. Crystal phase, excitation and emission spectra of sample phosphors are analyzed by means of XRD and FL, respectively. The emission spectra of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors exhibit four linear peaks attributed to the ⁵D₄?→?⁷F_J (J?=?6–3) transition of Tb³⁺ while four broad emission bands are observed in the emission spectra of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The effects of Eu²⁺ concentration on the luminescent properties of Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) are studied. Ce³⁺ affects the luminescent properties of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors just as the sensitizer. However, Eu²⁺ is considered both as the sensitizer and the activator in Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The chromaticity coordinates of Eu²⁺ and Tb³⁺ co-doped phosphors gather around the white light field with the CCT approximate to 5000 K, indicating that the luminescent property of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors may approach to a desired level needed for white LED application.     

Effects of fluxes on the synthesis of Ca3Sc2Si3O12:Ce3+ green phosphors for white light-emitting diodes

Different fluxes were added in preparation of Ca₃Sc₂Si₃O₁₂:0.01Ce³⁺ phosphors with a solid-state method and the different influences of the fluxes on phase formation, morphology, and photoluminescence properties of the phosphors were studied. The results show that CaF₂ flux is the best flux as it can decrease single phase-forming temperature, improve morphology and enhance photoluminescence of the Ca₃Sc₂Si₃O₁₂:0.01Ce³⁺ phosphors remarkably. White light-emitting diode was fabricated with the Ca₃Sc₂Si₃O₁₂:0.01Ce³⁺ phosphor prepared with CaF₂ flux, and good performances of this WLED confirm that CaF₂ is a good flux for preparing Ca₃Sc₂Si₃O₁₂:Ce³⁺, and the phosphor is an efficient green component for fabrication of white LEDs.     

Tunable color emitting of CaAl2Si2O8: Eu,Tb phosphors for light emitting diodes based on energy transfer

A series of single-phased CaAl₂Si₂O₈: Eu, Tb phosphors have been synthesized at 1400 °C via a solid state reaction. The emission bands of Eu²⁺ and Eu³⁺ were observed in the air-sintered CaAl₂Si₂O₈: Eu phosphor due to the self-reduction effect. Tb³⁺ ions that typically generated green emission were added in CaAl₂Si₂O₈: Eu phosphor for contributing for a wider-range tunable emission. Energy transfer from Eu²⁺ to Tb³⁺ and the modulation of valence distribution of Eu²⁺/Eu³⁺ that contributes to the tunable color emitting were elucidated. More importantly, a white emission can be obtained by controlling the codoped contents of Li⁺ as well as suppressing the self-reduction degree of Eu. The white light emitting with the color coordinate (0.326, 0.261) was obtained, which indicates that CaAl₂Si₂O₈: Eu, Tb is a promising tunable color phosphor for application in ultraviolet light emitting diodes (UV-LEDs).     

RE3+ (RE = Ce3+, Tb3+) doped BaGdF5 nanocrystals: Synthesis,optical and magnetic properties,and energy transfer

Through a citric acid assisted hydrothermal method, the RE³⁺ (RE³⁺ = Ce³⁺, Tb³⁺) doped cubic phase BaGdF₅ nanocrystals with a sphere-like morphology and an average size of 30 nm have been synthesized. The samples show paramagnetic properties at 300 K. The photoluminescence spectra of the obtained samples suggest that the existence of Ce³⁺ can dramatically enhance the emission intensity of Tb³⁺ due to an efficient energy transfer from Ce³⁺ to Tb³⁺. The energy transfer efficiency from Ce³⁺ to Tb³⁺, the critical energy transfer distance between Ce³⁺ and Tb³⁺, and the energy transfer mechanism of Ce³⁺–Tb³⁺ are discussed based on the experimental data and the theoretical analysis.