Cooperative energy transfer and frequency upconversion in Yb3+-Tb 3+ and Nd 3+-Yb 3+-Tb 3+ codoped GdAl3(BO3)4 phosphors

Polycrystalline GdAl₃(BO₃)₄ phosphors codoped with Yb³⁺/Tb³⁺ and/or Nd³⁺/Yb³⁺/Tb³⁺ have been synthesized by combustion method. Upon excitation with a 980 nm laser diode, an intense green upconversion luminescence has been observed in GdAl₃(BO₃)₄:Yb,Tb phosphor. The quadratic dependence of the luminescence on the pump-laser power indicating a cooperative energy transfer process. Meanwhile, it is noticed that upon excitation with 808 nm laser diode, intense luminescence has clearly been detected in GdAl₃(BO₃)₄:Nd,Yb,Tb phosphor. The luminescence intensity exhibits also a quadratic dependence on incident pump-laser power. However, no green-emission has been observed in GdAl₃(BO₃)₄ phosphors codoped with Yb³⁺/Tb³⁺ or Nd³⁺/Tb³⁺ respectively upon excited at 808 nm laser diode. A proposed upconversion mechanism involving energy transfer from Nd³⁺ to Yb³⁺, and then a cooperative energy transfer process from two excited Yb³⁺ to Tb³⁺ has been presented.     

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.     

LaOBr:Tb3+，Dy3+的发光特性及高压研究

 采用高温常压方法合成了稀土发光材料LaOBr:Tb³⁺，Dy³⁺，采用高温高压方法对材料进行了处理，研究了高温高压处理前后样品发光特性的变化，并进行了发光衰减测量。结果表明，Dy³⁺的掺杂可以将Tb³⁺的⁵D₃能级的激发能有效地驰豫到⁵D₄能级，从而使⁵D₄~⁷F_J（J＝0, 1,…,6）的发射，尤其是⁵D₄~⁷F₅的发射明显增强，使得样品的发光亮度大大提高。Dy³⁺，Tb³⁺间存在交叉驰豫共振能量传递。高压处理过程引入的杂质、材料氧化及压致晶场变化都对材料的发光特性产生影响。     

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.     

Photoluminescence and efficient energy transfer from Ce3+ to Tb3+ or Mn2+ in Ca9ZnLi(PO4)7 host

Structural and spectroscopic characterizations of the Ce³⁺/Tb³⁺(Mn²⁺) solely and Ce³⁺–Tb³⁺(Mn²⁺) doubly doped phosphate compound Ca₉ZnLi(PO₄)₇ with β-Ca₃(PO₄)₂ structure have been performed by powder X-ray diffraction and photoluminescence spectra measurements. The weak green emission from Tb³⁺ and red emission from Mn²⁺ are significantly enhanced by introduction of sensitizer Ce³⁺ ions due to an efficient resonant-type energy transfer from Ce³⁺ to activators Tb³⁺ or Mn²⁺. The energy transfer efficiency and the mechanism have been estimated based on spectroscopic data. Meanwhile, the critical distances for energy transfer between the Ce³⁺ and Tb³⁺ or Mn²⁺ ions are also calculated by the method of spectral overlapping.     

Diffusion-limited energy transfer from Tb3+ → Nd3+ and Tb3+ → Ho3+ in DMSO

The energy transfer phenomenon has been studied from Tb³⁺ → Nd³⁺ and Tb³⁺ → Ho³⁺ in DMSO. A diffusion limited dipole-dipole mechanism of energy transfer is suggested for both systems. At high acceptor concentrations, P_da depends linearly on C² consistent with the Fong and Diestler theory of energy transfer. However, at low acceptor concentrations the observations of time evolutions of Tb³⁺ luminescence decay following flash excitation has enabled us to examine diffusion limited energy transfer from Tb³⁺ to Nd³⁺ and Tb³⁺ to Ho³⁺ in DMSO.     

Luminescence and energy transfer in phosphor LiAl5O8: Ce3+, Dy3+

Ce³⁺ and Dy³⁺-doped LiAl₅O₈ were synthesized in the present study. The luminescence properties of Ce³⁺ and Dy³⁺, and the energy transfer from Ce³⁺ to Dy³⁺ were investigated. The Ce³⁺ species in LiAl₅O₈ emit one broad band that peaks at 351 nm under the excitation of ultraviolet light, which is attributed to the 5d–4f transitions of Ce³⁺. The luminescence of Dy³⁺ in singly doped LiAl₅O₈ can not be detected due to its low oscillator strength. However, Dy³⁺ emit intense blue (477 nm) and yellow (569 nm) light after the introduction of Ce³⁺. This phenomenon demonstrates that there exists effective energy transfer from Ce³⁺ to Dy³⁺, which occurs because the emission spectrum of Ce³⁺ perfectly overlays the excitation spectrum of Dy³⁺. The energy transfer from Ce³⁺ to Dy³⁺ is performed through dipole–dipole interactions. The experimental results show that LiAl₅O₈ co-doped with Ce³⁺ and Dy³⁺ can be a potential two-band (blue and yellow) phosphor.     

Energy transfer in CaSiO3 phosphors doped with Ce3+ and Tb3+

Calcium metasilicate phosphors activated by Ce³⁺ and Tb³⁺ have been studied for their emission characteristics. In two series of phosphors, one activator was kept at its optimum value while the other was varied. In another two series, one activator was kept below its optimum value and the other was varied. Concentration quenching effects start when each activator gives its maximum emission. There is clear evidence of an energy transfer from Ce³⁺ to Tb³⁺ because the⁵ D ₃ lines appear on addition of Ce³⁺ while they were conspicuously absent when Tb³⁺ alone was present. Their absence in singly activated phosphors could not have been due to cross-relaxation. Obviously X-ray excitation does not lead to⁵ D ₃ transitions which are achieved only by energy transfer. Further, considering the features of the emission spectra and the concentrations of activators used, the transfer could only be of the dipole-dipole type.     

VUV-UV excited luminescent properties of LnCa4O(BO3)3:RE (Ln=Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa₄O(BO₃)₃:RE³⁺ (LnCOB:RE, Ln=Y, La, Gd, RE=Eu, Tb, Dy, Ce) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos’ and Jφrgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. Jφrgensen, Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E_ct were calculated and compared with their excitation spectra.Eu³⁺ and Tb³⁺ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce³⁺ ions do not show efficient luminescence and quench the luminescence of Tb³⁺ ions when Tb³⁺ and Ce³⁺ ions are co-doped into LnCOB. GdCOB doped with Dy³⁺ shows yellowish white light under irradiation of 254 nm light for the reason that Gd³⁺ ions transfer the energy from itself to Dy³⁺. Because of the existence of Gd³⁺, the samples of GdCOB:RE³⁺ show higher excitation efficiency than LaCOB:RE³⁺ and YCOB:RE³⁺, around 188 nm, which indicates that the Gd³⁺ ions have an effect on the host absorption and can transfer the excitation energy to the luminescent center such as Tb³⁺, Dy³⁺ and Eu³⁺.     

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.     

Energy transfer from Tb3+ to Eu3+ ions sorbed on SrTiO3 surface

The energy transfer at room temperature between Tb³⁺ and Eu³⁺ ions sorbed onto SrTiO₃ powders is investigated, using Time-Resolved Laser-induced Fluorescence Spectroscopy (TRLFS). Several published works deal with the energy transfer between two lanthanide ions in co-doped matrices but it is the first time that transfer processes between two lanthanide ions sorbed on a solid surface is reported. The results show that the energy transfer between sorbed Tb³⁺ and Eu³⁺ ions on strontium titanate is a non-radiative process and follows a dipole–dipole type interaction. Moreover, the higher the acceptor ions Eu³⁺ concentration, the more efficient the energy transfer.It is shown that no energy migration between the Tb³⁺ donor ions occurs. A formalism based on the model of Inokuti–Hirayama is used and allows one to fit the non-exponential Tb³⁺ fluorescence decay. It is thus possible to evaluate the critical radius (R₀) of the influence sphere of the sorbed Tb³⁺ ions. According to the previous works, two sorption sites are considered for the sorbed rare-earth. The calculated radii are similar to those obtained for other couples of donor–acceptor lanthanide ions reported in the literature.     

Effect of temperature on quantum efficiency of energy transfer from Dy3+ to Er3+ in dimethylsulphoxide

Energy transfer has been studied from Dy³⁺ to Er³⁺ in DMSO at various temperatures. From the variation in the fluorescence yield and decay time of Dy³⁺ with varying concentration of Er³⁺, a dipole-dipole interaction mechanism of energy transfer is suggested from Dy³⁺ to Er³⁺ at various temperatures. The energy transfer is found to be efficient at 333 K.     

Ca8Mg(SiO4)4Cl2:Ce3+, Tb3+: A potential single-phased phosphor for white-light-emitting diodes

A single-phased white-light-emitting phosphor Ca₈Mg(SiO₄)₄Cl₂:Ce³⁺, Tb³⁺ (CMSC:Ce³⁺, Tb³⁺) is synthesized by a high temperature solid-state reaction method, and its photoluminescence properties are investigated. The obtained phosphor exhibits a strong excitation band between 250 and 410 nm, matching well with the dominant emission band of a UV light-emitting-diode (LED) chip. Energy transfer from Ce³⁺ to Tb³⁺ ions has been investigated and demonstrated to be a resonant type via a dipole–dipole mechanism. The energy transfer efficiency as well as the critical distance is also estimated. Furthermore, the phosphors can generate light from yellow-green through white and eventually to blue by properly tuning the relative ratio of Ce³⁺ to Tb³⁺ ions grounded on the principle of energy transfer. The results show that this phosphor has potential applications as a single-phased phosphor for UV white-light LEDs.     

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.     

Highly efficient cooperative energy transfer from Ho3+ and Tm3+ ions to Ce3+ ions in crystals

A phenomenon of highly efficient cooperative energy transfer from Ho³⁺ and Tm³⁺ ions to two-particle (2Ce³⁺) cooperative acceptors in crystals of solid solutions of La_1?x Ce _x F₃ is revealed. The rates of cooperative energy transfer in Ho³⁺→2Ce³⁺, Tm³⁺→2Ce³⁺, and Tb³⁺→ 2Yb³⁺ systems are measured, as well as their dependence on the magnitude of the matrix elements of donor transition.     

Enhancement of Tb emission by non-radiative energy transfer from Dy in silicate glass

A study of energy transfer was performed in dysprosium-terbium-doped silicate glasses at room temperature. Enhancement of the Tb³⁺ emission and a decrease in the Dy³⁺ emission are observed as a result of energy transfer from Dy³⁺ ions to Tb³⁺ ions. The energy transfer efficiencies, transfer probabilities, as well as average donor-acceptor distances were also calculated. It is concluded that the energy transfer mechanism between Dy³⁺ and Tb³⁺ ion is mainly electric dipole-dipole in nature.     

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 of Ln3+ and WO 2 2+ ions in wolframylphosphate glasses

We investigate the luminescent properties of potassium wolframylphosphate glasses doped with Eu³⁺, Tb³⁺, and Dy³⁺ ions whose luminescence is excited by donor-acceptor interaction between the active WO ₂ ²⁺ and Ln³⁺ ions, as well as the migration of energy in the subsystems of each type of the active ions. Comparison of the obtained data with the results of investigation of the spectroscopic properties of Ln³⁺ in uranylphosphate materials shows that a sufficiently high degree of the ionicity of bonds of Ln³⁺ with the atoms of its first coordination sphere is preserved in wolframylphosphate matrices. We show that three stages of the decomposition of electron excitations are typical of the WO ₂ ²⁺ ions in wolframylphosphate glasses doped with Ln³⁺ and two stages in nonactivated glasses. The electron excitation energy transfer in the WO ₂ ²⁺ −Ln³⁺ system occurs due to induction-resonance interaction. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 620–625, September–October, 1997.     

White light emission from sonochemically synthesized rare earth doped ceria nanophosphors

Undoped CeO₂, and single and triple doped CeO₂:M (where M=Dy³⁺, Tb³⁺and Eu³⁺) nanophosphors were synthesized through a simple sonochemical process and characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), EDS and photoluminescence (PL) spectrophotometry. The TEM micrographs show that resultant nanoparticles have flower-like shape. The doped samples showed multicolor emission on single wavelength excitation. Energy transfer was observed from host to the dopant ions. Characteristic blue emission from Dy³⁺ ions, green from Tb³⁺ ions and red from Eu³⁺ ions were observed. The CIE coordinates of the triple doped Ce_0.86Dy_0.005Tb_0.055Eu_0.08O₂ nanoflowers lie in the white light region of the chromaticity diagram and show promise as good phosphor materials for new lighting devices.     

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.