Effect of Tb3+ concentration on luminescence properties of Ce/Tb/Eu co-doped borosilicate glasses for white LEDs

Ce, Tb and Eu single and ternary doped borosilicate glasses were prepared and effect of Tb³⁺ concentration on luminescence properties of ternary co-doped glasses were analyzed by utilizing emission spectra, excitation spectra, the Commission International de I’Eclairage (CIE) colorimetric system and fluorescence decay curves. The results show that Tb³⁺ concentration significantly affects spectral intensities of ternary co-doped glasses when excited by near ultraviolet (NUV). With the increasing of Tb³⁺ concentration, the blue emission of Ce³⁺ is weakened and the red emission of Eu³⁺ is slightly enhanced. Both the color coordinates and correlated color temperatures (CCTs) can be adjusted by Tb³⁺ concentration. Besides, the energy transfers from Ce³⁺ to Tb³⁺ and from Tb³⁺ to Eu³⁺ were observed. Measured characteristic lifetimes of Tb³⁺ indicate that the energy transfer from Ce³⁺ to Tb³⁺ tends to predominate in whole process. The studies show that Ce/Tb/Eu ternary doped borosilicate glasses might be promising luminescence materials for NUV pumped white LEDs.     

Synthesis and luminescence properties of Tb:NaGd(WO4)2 novel green phosphors

Tb³⁺:NaGd(WO₄)₂ (Tb:NGW) phosphors with different Tb³⁺ concentrations have been synthesized by a mild hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence excitation and emission spectra and decay curve were used to characterize the Tb:NGW phosphors. XRD analysis confirmed the formation of NGW with scheelite structure. SEM study showed that the obtained Tb:NGW phosphors appeared to be nearly spherical and their sizes ranged from 1 to 1.5 μm. The excitation spectra of these systems showed an intense broad band with maximum at 270 nm related to the O→W ligand-to-metal charge-transfer state. Photoluminescence spectra indicated the phosphors emitted strong green light centered at 545 nm under UV light excitation. Analysis of the photoluminescence spectra with different Tb³⁺ concentrations revealed that the optimum dopant concentration for Tb³⁺ is about 15 at% of Tb³⁺ ions in Tb:NGW phosphors.     

Excited state dynamics and energy transfer rates in Sr3Tb0.90Eu0.10(PO4)3

The emission spectrum of neat Sr₃Tb(PO₄)₃ upon excitation at 337 nm in the levels above ⁵D₃ is dominated by ⁵D₄ emission and no significant emission from ⁵D₃ is observed due to efficient cross relaxation involving the Tb³⁺ levels. On the other hand, the emission spectrum of the same host containing 10 mol% Eu³⁺ upon excitation at the same wavelength (in the Tb³⁺ levels) is dominated by strong emission bands from the ⁵D₀ level of Eu³⁺. This clearly indicates that Tb³⁺→Eu³⁺ energy transfer is present. The excitation spectrum of the Eu^{3+ 5}D₀ emission is dominated by Tb³⁺ bands extending in the UV region.The presence of 10 mol% Eu³⁺ in Sr₃Tb(PO₄)₃ very strongly shortens the ⁵D₄ decay time. The decay curve is not far from exponential, indicating that the energy transfer to Eu³⁺ is accompanied by fast energy migration. The transfer regimes are identified and the donor–donor and donor–acceptor transfer microparameters are quantified under the assumption of electric dipole–electric dipole interactions.     

Rare earth ions doped full-color luminescence glasses for white LED

Silicate and phosphate glasses co-doped with rare-earth ions (REIs)(Ce³⁺, Tb³⁺, Eu³⁺) are presented in the present work. Their photoluminescence properties were studied by excitation and emission spectra. A combination of blue, green and red bands is shown for both silicate and phosphate glasses that allows the observation of white light when the glass is excited by UV light. The relative emission intensity ratios of the green to the red can be tuned by varying the concentrations of activator and/or sensitizer as well as the composition of glass matrices.     

Tb3+掺杂硅酸盐玻璃发光性能的浓度依赖关系

 利用高温熔融法制备了不同浓度的Tb³⁺掺杂硅酸盐玻璃,并分别测量了紫外和X射线激发时的发射光谱。光谱结果表明,不同浓度Tb³⁺掺杂硅酸盐玻璃在紫外和X射线激发时发光行为具有相似的浓度依赖关系：低浓度Tb₄O₇掺杂时主要以蓝光(5D₃→⁷FJ)发射为主,而高浓度掺杂时以绿光(⁵D₄→⁷FJ)发射为主。Tb³⁺发光强度与掺杂浓度的关系分析表明,⁵D₃的浓度猝灭是电偶极-电偶极相互作用引起的, 而⁵D₄的浓度猝灭是交换相互作用引起的。     

Effects of Tb doping on the photoluminescence of Y2O3:Tb nanophosphors

The effects of Tb doping on the photoluminescence (PL) of Y₂O₃:Tb nanophosphors have been investigated. Nanophosphors were prepared by the glycine-nitrate solution combustion technique using yttria and terbia powders as precursors. PL excitation spectra at room temperature consist of two overlapping bands centered at 277 and 304 nm, whereas emission spectra comprise several groups of lines corresponding to the ⁵D₄→⁷F_J (J=1-6) 4f electronic transitions of the Tb⁺³ ions. A direct comparison of nanophosphor and bulk concentration-quenching curves was obtained by annealing the nanophosphor powder and converting it to bulk material without altering the Tb concentration. The peak in the nanophosphor concentration-quenching curve occurs at a concentration ∼3 times higher than that of the bulk.     

Double emitting phosphor NaSr4(BO3)3:Ce, Tb for near-UV light-emitting diodes

Blue and green double emitting phosphor, Ce³⁺ and Tb³⁺ co-doped NaSr₄(BO₃)₃, was synthesized in a weak reducing atmosphere by a conventional high temperature solid-state reaction technique. For comparison, Ce³⁺ or Tb³⁺ singly doped NaSr₄(BO₃)₃ was also prepared. The emission and excitation spectra of all samples have been investigated. NaSr₄(BO₃)₃:Tb³⁺ excitation includes a strong absorption at about 240 nm and some weak sharp lines in near-ultraviolet (n-UV) spectral region. The excitation of Ce³⁺ and Tb³⁺ co-doped NaSr₄(BO₃)₃ shows a strong broad band absorption in the n-UV region from the contribution of Ce³⁺, which makes it suitable for excitation by a n-UV LED chip. The emission of NaSr₄(BO₃)₃:Ce³⁺,Tb³⁺ consists of a blue emission band from Ce³⁺ and a green emission from Tb³⁺ under the excitation of n-UV light. Energy transfer between Ce³⁺ and Tb³⁺ is also discussed, and the relative intensity of blue emission and green emission could be tuned by adjusting the concentration of Ce³⁺ and Tb³⁺. The phosphor NaSr₄(BO₃)₃:Ce³⁺,Tb³⁺ could be considered as a double emission phosphor for n-UV excited white light-emitting diodes.     

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.     

New promising phosphors Ba3InB9O18 activated by Eu/Tb

Borate Ba₃InB₉O₁₈ (BIBO) has been adopted as a host material for phosphors for the first time. Lanthanide ions (Eu³⁺/Tb³⁺)-doped BIBO phosphors have been synthesized by solid-state reaction and luminescent properties investigated under ultravoilet (UV) excitation. For red phosphor BIBO:Eu, dominant emission peaking at 590 nm was attributed to ⁵D₀→⁷F₁ transition of Eu³⁺, which confirmed that the local site of Eu³⁺ occupied by In³⁺ ion in BIBO crystal lattice is at inversion symmetry center. Optimum Eu³⁺ concentration of BIBO:Eu under UV excitation with 227 nm wavelength is around 40%. The green phosphor BIBO:Tb showed bright green emission at 550 with 232 nm light excited and optimal of Tb³⁺ concentration measured in BIBO is about 8%. The corresponding luminescence mechanisms of Ln-doped BIBO (Ln=Eu³⁺/Tb³⁺) were analyzed. The luminescent intensity of Tb³⁺ can be significantly improved by co-doping of Bi³⁺ in the BIBO:Tb lattice. The likely reason was proposed in terms of the different interactions of the host lattice with these ions, and of these ions with each other.     

Luminescent properties and energy transfer of double-emitting NaSrPO4:Eu2+,Tb3+ phosphor for near-UV white LEDs

Novel blue/green NaSrPO₄ phosphors co-doped with Eu²⁺ and Tb³⁺ were synthesized by a conventional solid-state reaction. Their luminescent properties were characterized by using powder X-ray diffraction, photoluminescence excitation and emission spectra, lifetime, and temperature dependent emission spectra, respectively. The NaSrPO₄:Eu²⁺,Tb³⁺,Na⁺ phosphor showed an intense broad excitation band between 250 and 430 nm, which was in agreement with the near-UV chip (350–420 nm), and it exhibited two dominating emission bands at 445 and 545 nm, corresponding to the allowed 4f⁶5d¹→4f⁷(⁸S_7/2) transition of Eu²⁺ ion and the ⁵D₄→⁷F₅ transition of Tb³⁺ ion, respectively. The emission intensity and lifetime of Eu²⁺ ion decreased with the increasing concentration of Tb³⁺ ion, which strongly indicated that an effective energy transfer occurred from Eu²⁺ to Tb³⁺ in NaSrPO₄ host. The principle of the energy transfer should be the combined effect of the non-radiative resonant energy transfer and the phonon-assisted non-radiative process.     

Eu/Tb ions co-doped white light luminescence Y2O3 phosphors

Y₂O₃:Eu³⁺, Tb³⁺ phosphors with white emission are prepared with different doping concentration of Eu³⁺ and Tb³⁺ ions and synthesizing temperatures from 750 to 950 °C by the co-precipitation method. The resulted phosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. The results of XRD indicate that the crystallinity of the synthesized samples increases with enhancing the firing temperature. The photoluminescence spectra indicate the Eu³⁺ and Tb³⁺ co-doped Y₂O₃ phosphors show five main emission peaks: three at 590, 611 and 629 nm originate from Eu³⁺ and two at 481 and 541 nm originate from Tb³⁺, under excitation of 250-320 nm irradition. The white light luminescence color could be changed by varying the excitation wavelength. Different concentrations of Eu³⁺ and Tb³⁺ ions were induced into the Y₂O₃ lattice and the energy transfer from Tb³⁺→Eu³⁺ ions in these phosphors was found. The Commission International de l’Eclairage (CIE) chromaticity shows that the Y₂O₃:Eu³⁺, Tb³⁺ phosphors can obtain an intense white emission.     

Ultraviolet and visible upconversion emission in Tb3+/Yb3+ co-doped fluorophosphate glasses

Ultraviolet and visible upconversion emissions in Tb³⁺/Yb³⁺ co-doped YF₃–BaF₂–Ba(PO₃)₂ glasses were observed under 980-nm laser diode excitation. The dependence of the emission intensities of Tb³⁺ on the pump power reveals that two-photon processes account for blue cooperative emission of Yb³⁺ at 476 nm and green upconversion emission of Tb³⁺ at 543 nm, and three-photon processes for ultraviolet emission of Tb³⁺ in the wavelength range of 379–435 nm. The effects of Tb³⁺ concentration on the emission intensity and the lifetime of Tb³⁺ and Yb³⁺ are investigated in detail. It is found that the cooperative energy transfer from a pair of excited Yb³⁺ ions to a ground Tb³⁺ ion is responsible for the appearance of blue and green upconversion emissions due to the ⁵D₄→⁷F _J (J=6,5,4,3) transitions of Tb³⁺, and the resonance energy transfer from Yb³⁺ to Tb³⁺ accounts for the population on the ⁵D₃,⁵G₆ level and ultraviolet upconversion emission.     

Down-conversion process in Tb3+–Yb3+ co-doped Calibo glasses

The down-conversion process in Tb³⁺–Yb³⁺ co-doped Calibo glasses was studied. The emission, excitation and time-resolved measurements indicated the existence of an energy conversion through the excitation of Tb³⁺ ions to near-infrared emission by Yb³⁺ ions. The emission intensity dependence on excitation power confirms that the one-photon process is responsible for the Yb³⁺ emission. An enhanced Yb³⁺ emission was observed with Yb³⁺ doping and an optimal energy transfer efficiency of 32% was obtained before reaching near-infrared emission quenching. The mechanism of the non-resonant energy transfer from Tb³⁺ to Yb³⁺ is discussed in terms of the Tb³⁺–Yb³⁺ cross-relaxation and multiphonon decay processes.     

Feasibility Study of VUV Sensitization Effect of Tb3+

The possibility to use Tb³⁺ as luminescence sensitizer for enhancement of the conversion efficiency of vacuum-ultraviolet (VUV) radiation into visible light was examined. We studied the luminescence properties of K₃Tb(PO₄)₂ and Ba₃Tb(PO₄)₃ activated by Eu³⁺, and of SrAl₁₂O₁₉ co-doped with Mn²⁺ and Tb³⁺ at excitation over the 120 to 300 nm wavelength range. It is shown that Tb³⁺ ions, exhibiting a strong absorption band in the VUV, can provide efficient sensitization of Eu³⁺ and Mn²⁺ emissions for excitation in this spectral range, giving rise to intense red and green luminescence, respectively. This study provides a proof for the concept of VUV sensitization, which enables the engineering of luminescence materials with improved efficiency for excitation from a noble gas discharge.     

Luminescent features of sol–gel derived rare-earth multi-doped oxyfluoride nano-structured phosphors for white LED application

Rare-earth doped oxyfluoride 75SiO₂:25PbF₂ nano-structured phosphors for white-light-emitting diodes were synthesized by thermal treatment of precursor sol–gel derived glasses. Room temperature luminescence features of Eu³⁺, Sm³⁺, Tb³⁺, Eu³⁺/Tb³⁺, and Sm³⁺/Tb³⁺ ions incorporated into low-phonon-energy PbF₂ nanocrystals dispersed in the aluminosilicate glass matrix and excited with UV light emitting diode were investigated. The luminescence spectra exhibited strong emission signals in the red (600, 610, 625, and 646 nm), green (548 and 560 nm), and blue (485 nm) wavelength regions. White-light emission was observed in Sm/Tb and Eu/Tb double-doped activated phosphors employing UV-LED excitation at 395 nm. The dependence of the luminescence emission intensities upon annealing temperature and rare-earth concentration was also examined. The results indicated that there exist optimum annealing temperature and activator ion concentration in order to obtain intense visible emission light with high color rendering index. The study suggests that the nanocomposite phosphor based upon 75SiO₂:25PbF₂ host herein reported is a promising contender for white-light LED applications.     

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.     

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.     

Charge compensation on the luminescence properties of ZnWO4:Tb phosphors via hydrothermal synthesis

A phosphor Tb³⁺-doped ZnWO₄ (ZWO:Tb) phosphors were prepared by a hydrothermal method. X-ray powder diffraction (XRD) analysis revealed that the as-obtained sample is pure ZnWO₄ phase. The excitation and emission spectra indicated that the phosphor could be well excited by ultraviolet light (272 nm) and emit blue light at about 491 nm and green light at about 545 nm. Significant energy transfer from WO₄²⁻ groups to Tb³⁺ ions has been observed. Two approaches to charge compensation are investigated: (a) 2Zn²⁺ = Tb³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Zn²⁺ = 2Tb³⁺ + vacancy. Compared with two charge compensation patterns in the ZnWO₄:Tb³⁺, it has been found that ZnWO₄:Tb³⁺ phosphors used Li⁺ as charge compensation show greatly enhanced bluish-green emission under 272 nm excitation.     

Concentration-dependent luminescence of Tb ions in high calcium aluminosilicate glasses

This study deals with the results on the concentration-dependent fluorescence properties of Tb³⁺-doped calcium aluminosilicate (CAS) glasses of composition (100−x)(58SiO₂–23CaO–5Al₂O₃–4MgO–10NaF in mol%)-x Tb₂O₃ (x=0, 0.25, 0.5, 1, 2, 4, 8, 16, 24, 32, 40 in wt%). The FTIR reflectance spectra suggested the role of dopant ions as network modifiers in the glass network. The fluorescence spectra of low Tb³⁺-doped glasses have revealed prominent blue and green emissions from ⁵D₃ and ⁵D₄ excited levels to ⁷F_j ground state multiplet, respectively. The glass with 2 wt% of Tb₂O₃ has exhibited maximum intensity of blue emission from ⁵D₃ level, while green emission from ⁵D₄ level has increased linearly up to 24 wt% and showed reduction in the rate of increase for higher Tb₂O₃ concentrations. The concentration quenching of blue emission (⁵D₃→⁷F_j) is attributed mainly to the resonant energy transfer (RET) assisted cross-relaxation (CR) among the excited and nearest neighbour unexcited Tb³⁺ ions in the glass matrix. The decline in rate of increase of green emission (⁵D₄→⁷F_j) at higher concentrations has been explained due to a possible occurrence of cooperative energy transfers leading to 4f⁸→4f⁷5d transition interactions. The blue and green emission decay kinetics have been recorded to compute the excited level (⁵D₃ and ⁵D₄) lifetimes, which confirmed the Tb³⁺ concentration quenching of the blue emission in these glasses.