Na2SrMg(PO4)2: Ce3+, Mn2+荧光粉的发光性质及其能量传递机理

采用高温固相法制备了Na₂SrMg(PO₄)₂: Ce³⁺, Mn²⁺ (NSMP: Ce³⁺, Mn²⁺) 荧光粉, 并对其发光性质及Ce³⁺ 对Mn²⁺ 的能量传递机理进行了研究. Ce³⁺ 和Mn²⁺ 在334 nm 和617 nm 的发射峰分别为Ce³⁺ 的5d→4f 跃迁和Mn²⁺ 的⁴T₁(⁴G)→⁶A₁(⁶S) 跃迁产生. Ce³⁺ 对Mn²⁺ 的发光有较强的敏化作用, 根据Dexter能量传递效率公式判断Na₂SrMg(PO₄)₂ 中Ce³⁺ 对Mn²⁺ 的能量传递属于电偶极-电四极相互作用引起的共振能量传递.     

White light generation through the zinc metaphosphate glass activated by Ce, Tb and Mn ions

The photoluminescence of Ce³⁺, Tb³⁺ and Mn²⁺ ions was investigated in the Zn(PO₃)₂ glass. The blue and green emissions of Tb³⁺ ions and the red emission of Mn²⁺ ions are enhanced upon UV excitation through a non-radiative energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions. The efficiency of this transfer was estimated in at least 62%. It is demonstrated that this glass activated with three ions (Ce³⁺, Tb³⁺ and Mn²⁺) can generate white light emission (x=0.420 and y=0.423 chromaticity coordinates and 3440 K colour temperature) under excitation at 254 nm, i.e., using an AlGaN-based LED as excitation source.     

Energy transfer mechanisms in the KCaLa1−x−yCexTby(PO4)2 phases

The various mechanisms involved in the green emission of KCaLa_1?x?yCe_xTb_y(PO₄)₂ under UV excitation are analyzed for a weak terbium concentration (y = 0.05). Ce³⁺ → Tb³⁺ transfer can be described by the Dexter model, but only for a weak cerium concentration. For higher cerium contents the cerium lifetime temperature dependence can be fitted by using a model involving energy migration between Ce³⁺ ions before Ce³⁺ → Tb³⁺ transfer. The investigation of the variation of the terbium emission vs temperature involves the presence of energy-trapping defects in the material.     

Luminescence properties of NaGd(PO3)4:Eu3+ and energy transfer from Gd3+ to Eu3+

The luminescence properties of polyphosphates NaEu _x Gd_(1?x)(PO₃)₄ (x = 0–1.00) and the energy transfer from Gd³⁺ to Eu³⁺ were studied. In undoped NaGd(PO₃)₄ sample, the photon cascade emission of Gd³⁺ was observed under ⁸S_7/2 → ⁶G_J excitation (201 nm) in which the emission of a red photon due to ⁶G_J → ⁶P_J transition is followed by an ultraviolet photon emission due to ⁶P_J → ⁸S_7/2 transition. When part of Gd³⁺ ions in the host NaGd(PO₃)₄ were substituted by Eu³⁺ ions, the NaGd(PO₃)₄:Eu³⁺ sample showed intensive red emission under 172-nm vacuum-ultraviolet (VUV) excitation which is suitable for mercury-free fluorescent lamps and plasma display panel applications. Based on the VUV–visible spectroscopic characteristics and the luminescence decay properties of NaGd(PO₃)₄:Eu³⁺, it was found that the quantum cutting by a two-step energy transfer from Gd³⁺ to Eu³⁺ can improve the red emission of Eu³⁺ ions under VUV excitation but only a part of the excitation energy in the excited ⁶P_J states within Gd³⁺ ions can be transferred to Eu³⁺ ions for its red emission, and the nonradiative energy transfer efficiencies from the excited ⁶P_J states within Gd³⁺ to Eu³⁺ were calculated.     

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.     

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.     

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.     

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.     

Photoluminescence properties of Ca9Lu(PO4)7:Ce3+, Mn2+ prepared by conventional solid-state reaction

A new red-emitting phosphor Ca₉Lu(PO₄)₇:Ce³⁺, Mn²⁺ has been synthesized by solid-state reaction, and its luminescence properties have been investigated. The broad red emission peaked at 645 nm of Mn²⁺ is greatly enhanced by the sensitizer Ce³⁺ due to efficient energy transfer from Ce³⁺ to Mn²⁺. The energy transfer was demonstrated to belong to a resonant type via a dipole–quadrupole mechanism. The critical distance for Ce³⁺→Mn²⁺ energy transfer was calculated to be 15.04 Å by concentration quenching method. Preliminary results indicate that the phosphor might be a promising red phosphor for UV-based white LEDs.     

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.     

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.     

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.     

Concentration dependence of the Ce3+ and Tb3+ luminescence of Ce1-xTbxMgAl11O19

The quenching of the Ce³⁺ emission and the increase of the Tb³⁺ emission with increasing x of Ce_1-xTb_xMgAl₁₁O₁₉ for x ? 0.35 is ascribed to energy transfer from Ce³⁺ to Tb³⁺, which is restricted to nearest rare earth neighbours. This transfer is almost complete at x ? 0.35. The decrease of the Tb³⁺ emission at higher Tb³⁺ concentrations is not due to Tb³⁺ concentrational quenching, but due to the limited solubility of Tb³⁺ in the CeMgAl₁₁O₁₉ phase.     

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.     

On the Luminescence of Ce<Superscript>3+</Superscript>, Eu<Superscript>3+</Superscript>, and Tb<Superscript>3+</Superscript> in Novel Borate LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>

This paper reports on the photoluminescence (PL) and time-resolved properties of Ce³⁺, Eu³⁺, and Tb³⁺ in novel LiSr₄(BO₃)₃ powder phosphors. Ce³⁺ shows an emission band peaking at 420 nm under 350-nm UV excitation. Energy transfer from Ce³⁺ to Mn²⁺ takes place in the co-doped samples. Eu³⁺ shows red emission under near UV excitation. LiSr₄(BO₃)₃:Eu³⁺ phosphor could be a suitable candidate for phosphor-converted solid state lighting. The luminescence lifetime is 2.13 ms for Eu³⁺ in LiSr₄(BO₃)₃:0.001Eu³⁺. As Eu³⁺ concentration increasing, the decay curves deviate from exponential behavior. Tb³⁺ shows the strongest ⁵D₄→⁷ F₅ emission line at 540 nm. Decay curves of ⁵D₄→⁷ F₅ and ⁵D₃→⁷ F₅ emission with different Tb³⁺ concentrations were also measured. Cross-relaxation process is discussed based on the decay curves.     

Luminescence of Mn ions in Tb3Al5O12 garnet

The paper is dedicated to investigation of the Mn²⁺ luminescence in Tb₃Al₅O₁₂ (TbAG) garnet, as well as the processes of excitation energy transfer between host cations (Tb³⁺ ions) and activators (Mn²⁺ and Mn²⁺-Ce³⁺ pair ions) in single crystalline films of TbAG:Mn and TbAG:Mn,Ce garnets which can be considered as promising luminescent materials for conversion of LED's radiation. Due to the effective energy transfer between TbAG host and activator, Mn²⁺ ions in TbAG possess the bright orange luminescence in the bands peaked at 595 nm with a lifetime of 0.64 ms which are caused by the ⁴T₁→⁶A₁ radiative transitions. The simultaneous process of energy transfer is realized in TbAG:Mn,Ce: (i) from Tb³⁺ to Mn²⁺ ions; (ii) from Tb³⁺ cations to Ce³⁺ ions and then partly to Mn²⁺ ions through Tb³⁺ ion sublattice and Ce-Mn dipole-dipole interaction.     

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.     

The energy transfer from Eu2+ to Tb3+ in calcium chlorapatite phosphor and its potential application in LEDs

Energy transfer from Eu²⁺ to Tb³⁺ was observed by investigating the optical properties from photoluminescence spectra and decay time curves in Tb³⁺ singly doped and Eu²⁺–Tb³⁺ co-doped calcium chlorapatite, Ca₅(PO₄)₃Cl (CPCl). It is dominated by the cooperation of a phonon-assisted energy transfer process and a non-radiative resonant energy transfer process caused by the exchange interaction. Eu²⁺–Tb³⁺ co-doped calcium chlorapatite phosphors in which Tb³⁺ can be efficiently excited by 400 nm are potential candidates for phosphor-converted LED.     

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.