Tunable emission,energy transfer and thermal stability of Ce3+, Tb3+ co-doped Na2BaCa(PO4)2 phosphors

A series of single Ce³⁺ doped and Ce³⁺ and Tb³⁺ co-doped Na₂BaCa(PO₄)₂ (NBCP) phosphors was synthesized by conventional solid-stated reaction method. The crystal structure, luminescence properties, thermal stability and energy transfer were carefully investigated. Ce³⁺ is inferred to substitute the Ba²⁺ site in NBCP lattice. The color-tunable emission from blue to green is observed by adjusting Tb³⁺ concentration among NBCP:0.03Ce³⁺,yTb³⁺ phosphors. The energy transfer behavior from Ce³⁺ to Tb³⁺ ions is both illustrated by co-doped PL spectra and decay curves. The energy transfer efficiency is as high as 91.5%. The mechanism of energy transfer is resonance type of dipole-dipole transition. In this work, the optimal phosphor exhibits the excellent thermal stability which keeps at 94.9% of that initial value at room temperature when temperature reaches to 150 °C. The Ce³⁺ and Tb³⁺ co-doped NBCP phosphor is a promising candidate for the application in the general lighting and display fields.     

A NIR to NIR rechargeable long persistent luminescence phosphor Ca2Ga2GeO7:Yb3+,Tb3+

Near infrared to near infrared (NIR–NIR) photo-stimulated persistent luminescence (PSPL) has shown excellent potential in high-resolution bioimaging for deep tissues. However, the PSPL in NIR-Ⅱ region (900–1700 nm) is still lacking. In this work, Ca₂Ga₂GeO₇:Yb³⁺,Tb³⁺ (CGGYT) phosphor with unique low-dimensional crystal structure was synthesized by high-temperature solid–state reaction. Thanks to the carriers transferring from deep traps to shallow ones induced by low energy light, the 978 nm PSPL originating from ²F_5/2 to ²F_7/2 transition of Yb³⁺ induced by multimode stimulating (980 nm or WLED) is successfully realized after pre-excited by UV lamp. The NIR PSPL of the specimen can be repeatedly stimulated after placed in dark for 12 h. Moreover, the results indicate that codoping with Tb³⁺ can significantly enhance the NIR-II PSPL owing to the quantum cutting persistent energy transfer (QC PET) from Tb³⁺ to Yb³⁺. Our study points to a new direction for the future development of multimode PSPL materials for bioimaging or multimode optical storage applications.     

Physicochemical properties of Li3Ba2La3(MoO4)8:Eu,Tb red-emitting phosphor for solid state white lamps

In this work,combustion synthesis was used for the first time to fabricate a phosphor material with red emission for applications in solid-state white-light lamps.We synthesized a material with emission wavelength at λ_em=617 nm,excited under long UV-blue wavelength based on Eu³⁺,Tb³⁺-activated molybdates Li₃Ba₂(La_1-x-yEu_xTb_y)₃(MoO₄)₈ with 0 ≤ x ≤1 and 0 ≤ y ≤ 1.A series of pow...     

Effectively enhanced photoluminescence of CePO4:Tb3+ nanorods combined with carbon dots

CePO₄:Tb³⁺ nanorods were successfully obtained via a simple hydrothermal method and combined with carbon dots (CDs) to obtain CDs@CePO₄:Tb³⁺ nanorods. Due to the combination of CDs, the emission intensity of CDs@CePO₄:Tb³⁺ nanorods increases about 92 times, compared with that of CePO₄:Tb³⁺ nanorods. The combination of CDs and CePO₄:Tb³⁺ nanorods was confirmed by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and so on. The mechanism of luminescence enhancement may be attributed to some aspects: the formation of hexagonal phase results in the increase of crystal field symmetry, and the energy transfer among CDs, Ce³⁺ and Tb³⁺ ions, which causes the Tb³⁺ ions in CDs@CePO₄:Tb³⁺ nanorods to obtain more excited energy and less non-radiative attenuation compared to CePO₄: Tb³⁺ nanorods. The luminescence enhancement strategy through combination of CDs would provide a simple and effective approach for other rare earth ions doped luminescent materials.     

Luminescence properties of BaAl12O19:Tb,Ce and energy transfer between Ce3+, Tb3+

BaAl₁₂O₁₉:Tb,Ce phosphors were prepared by sol-gel technique, the crystalline structures of samples characterized by XRD, and the luminescence properties and energy transfer between Ce³⁺ and Tb³⁺ were investigated. The results indicated that the emission intensity and the excitation wavelength range of Tb³⁺ increased when Ce³⁺ was doped. It demonstrated that the Ce³⁺ added in the BaAl₁₂O₁₉:Tb could deliver energy to Tb³⁺, and Ce³⁺ was not luminous by itself. The relative emission intensity of Tb³⁺ at wavelength of 548 nm was the strongest by Tb³⁺/Ce³⁺ ratio of 2:1, when excited at 310 nm, which was the characteristic adsorption wavelength of Ce³⁺.     

EXAFS study of cation reordering in NaYF4：Yb3＋,Tb3＋ up-conversion luminescence materials

The NaYF4：yb3＋,Tb3＋ （Xyb： 0.20, XTb： 0.04） materials were prepared using the co-precipitation method, lne as-preparea material was washed either with or without water in addition to ethanol and thereafter annealed for 5 h at 500℃. This resulted in materials with moderate or very high up-conversion luminescence intensity, respectively. The structural study carried out with X-ray powder diffraction revealed microstrains in the rare earth （R） sublattice that were relaxed for the material with very high up-conversion intensity thus decreasing energy losses. The local structural details were investigated with R LⅢ and Y K edge ex- tended X-ray absorption fine structure （EXAFS） using synchrotron radiation. Around 10 tool.% of the Yb3＋ ions were found to occupy the Na site in the material with very high up-conversion intensity. These Yb species formed clusters with the Tb3＋ ions occupying the regular Na/R sites. Such clustering enhanced the energy transfer between Yb3＋ and Tb3＋ thus intensifying the up-conversion emission.     

Bi3+ assisted luminescence in SrMoO4:Sm3+ red phosphors

In this paper, we report synthesis of pure SrMoO₄, Sm³⁺ (1 at%–5 at%) doped SrMoO₄ and Bi³⁺ (1 at%–3 at%) co-doped in 4 at% Sm³⁺ doped SrMoO₄ (SrMoO₄:4Sm³⁺) phosphors by solution combustion method. The X-ray diffraction (XRD) analysis reveals the tetragonal phase of all samples, also Bi³⁺ co-doping supports crystallite size growth and reduces lattice strain. Absorption analysis of Sm³⁺ doped SrMoO₄ ascertains a decrease in band gap and Bi³⁺ co-doping confirms the emergence of an absorbance peak at around 308 nm attributed to Bi³⁺ energy levels. Photoluminescence (PL) analysis ascertains an increase in emission peaks for Sm³⁺ doped SrMoO₄ up to 4% concentration, which are attributed to an electron transition from ⁴G_5/2 to ⁶H_J (J = 5/2, 7/2, 9/2, and 11/2) energy levels of Sm³⁺ ions. We have explained the effects of Bi³⁺ co-doping on the luminescence of Sm³⁺ doped SrMoO₄. The reduced microstrain and increased crystallinity of the phosphors as a result of Bi³⁺ co-doping and their correlation with the luminescence of Sm³⁺ ions are discussed.     

Hydrothermal synthesis,structure study and luminescent properties of YbPO4:Tb3+ nanoparticles

YbPO₄:Tb³⁺ were synthesized by mild hydrothermal method. The luminescent properties, morphologies and structure of the obtained powders were characterized by photoluminescence (PL) spectra, FESEM, X-ray diffractometer (XRD) and FTIR. The results showed that the prepared YbPO₄:Tb³⁺ nanoparticles were pure tetragonal phase and the average grain size varied with increasing of Tb³⁺ concentration. Hydrothermal temperature was revealed to be the key factor to enhance the emission intensity of YbPO₄:Tb³⁺ phosphors. The spherical nanoparticles could be effectively excited by near UV (369 nm) light and exhibited green performance at 543 nm (⁵D₄→⁷F₅), 489 nm (⁵D₄→⁷F₆) and 586 nm (⁵D₄→⁷F₄). The CIE chromaticity was calculated to be x=0.298, y=0.560. The YbPO₄:Tb³⁺ nanoparticles exhibited potential to act as UV absorber for solar cells to enhance the conversion efficiency.     

Upconversion multicolor tuning of NaY(WO4)2:Tb3+ with Eu3+ doping

A series of Tb~(3+) and Eu~(3+) co-doped NaY(WO_4)_2 phosphors were synthesized by hydrothermal reactions.The crystal structure,morphology,upconversion luminescent properties,the energy transfer from Tb~(3+) to Eu~(3+)ions and the ~5 D_4→ ~7 F_5 transition of the Tb~(3+) ion in NaY(WO_4)_2:Tb~(3+),Eu~(3+) phosphors were investigated in details.The results indicate that all the synthesized samples are of pure tetragonal phase NaY(WO_4)2.Furthermore,the micrometer-sized needle spheres and excellent dispersion of the particles are obtained by adding polyethylene glycol(PEG-2000) as the surfactant.Phosphors of NaY(WO_4)_2:Tb~(3+),Eu~(3+) exhibit the492 nm blue emission peak,546 nm green emission peak,595 nm orange emission peak and 616 nm red emission peak under 790 nm excitation.The energy transfer from Tb~(3+) to Eu~(3+) is a resonant transfer,in which electric dipole-dipole interaction plays a leading role.By adjusting the doping concentration of Eu~(3+) in NaY(WO_4)_2: 1.0 mol%Tb~(3+),xmol%Eu~(3+) phosphors,the emitting color of UC phosphors can be tuned from green to red.     

Energy transfer from Tb3+ to Eu3+ in zinc lead borate glass

In order to sensitize the luminescence of Eu³⁺ ions in heavy metal glass, zinc lead borate glass samples containing various concentrations of Eu³⁺ and Tb³⁺ ions were prepared to study the Tb³⁺ to Eu³⁺ non-radiative energy transfer phenomena. Energy level structures of Tb³⁺ and Eu³⁺ ions were plotted to show the excitation and energy transfer routes. Efficient energy transfer from Tb³⁺ to Eu³⁺ was observed and studied qualitatively in terms of doping concentrations. The sensitization turned out to be less effective than expected. Further studies to characterize the oxidation of Tb³⁺ into tetravalent state and to examine the mechanism of energy transfer are proposed.     

A single-phase full-color phosphor Sr2Ca2La(PO4)3O:Eu2+,Tb3+,Mn2+: Photoluminescence and energy transfer

A single-phase full-color emitting phosphor Sr₂Ca₂La(PO₄)₃O:Eu²⁺,Tb³⁺,Mn²⁺ was synthesized by the high temperature solid-state method. The phase formation, luminescence properties, thermal stability, and energy transfer from Eu²⁺ to Tb³⁺ and Eu²⁺ to Mn²⁺ in Sr₂Ca₂La(PO₄)₃O were investigated in details. Tunable emission color from blue to blueish green or orange can be observed under 365 nm near-ultraviolet excitation based on the energy transfer from Eu²⁺ to Tb³⁺ or Mn²⁺ ions by varying the ratio of Eu²⁺/Tb³⁺ or Eu²⁺/Mn²⁺ ions. White light was obtained with chromaticity coordinates of (0.3558, 0.3500) in the Sr₂Ca₂La(PO₄)₃O:0.04Eu²⁺,0.08Tb³⁺,0.40Mn²⁺ phosphor, suggesting their potential applications in white light emitting diodes.     

Structure and luminescence properties of color-tunable phosphor Sr2La3(SiO4)3F:Tb3+,Sm3+

A series of single-phase and color-tunable phosphors Sr₂La₃(SiO₄)₃F:0.15Tb³⁺,xSm³⁺(SLSOF:0.15Tb³⁺,xSm³⁺) was prepared using solid-state route.The X-ray diffraction(XRD) was used to characterize the phase of the as-prepared samples.The synthesized phosphors have apatite-type structure without other impurities.Sm³⁺ and Tb³⁺ ions substitute La³⁺ into the lattice and form a single...     

EXAFS investigation and luminescent properties of nanosized Tb: Lu2O3 phosphors

Nanosized terbium doped Lu2O3 phosphors were synthesized via a modified co-precipitation processing.The as-prepared Tb:Lu2O3 phosphors was consisted of well crystallized nanosized sphere particles with a diameter of about 30 nnx Local structure of Tb ions in Lu2O3 lattice was investigated by an analytical approach based on Fourier transformation of the extended X-ray absorption fine structure(EXAFS) data.X-ray near edge structure (XANES) spectra suggested that all Tb ions doped were tervalonce.EXAFS results indicated that Tb ions have entered the Lu2O3 cubic lattice by means of solid solution.The coordination number and first shell Tb-O distance dropped with the increasing of Tb concentration.Emission spectra of the phosphors was shown to be typical for Tb3+ with main components at 542,550 and 490 nm,derived from irradiative relaxation of 5D4 level.The emission intensity decreased severely with the increasing of Tb concentration from 1 mol.% to 15 tool.%,suggesting a significant concentration quenching above 1 mol.% Tb.The reduction of emission intensity was interpreted by higher distortion derived relaxation among the surface state resident Tb3+ ions.     

Down- and up-conversion processes in Nd3+/Yb3+ co-doped sodium calcium silicate glasses with concomitant Yb2+ assessment

Novel Nd³⁺/Yb³⁺ co-doped sodium calcium silicate glasses were prepared by melting quenching method:Spectroscopic study was carried out as a function of doping content by fixing sensitizer(Nd³⁺) concentration to 0.2 mol% and adjusting activator(Yb³⁺) from 0 to 1.0 mol%.The energy transfer(ET)mechanisms between Nd³⁺and Yb³⁺ are discussed based on their energy levels and excitation powerdependence emission intensity.Results show that...     

Effects of two strategies on afterglow behavior of Lu2O3:Eu single crystal scintillator:Co-doping with Pr3+ and solid solution with Sc2O3

In this paper,effect of two strategies on afterglow behavior of Lu₂O₃:Eu single crystal scintillato r,Pr³⁺ codoping and solid solution with Sc₂O₃,were studied systematically.Two groups of Lu₂O₃:5 at%Eu,x at%Pr(x=0,0.2,0.5,1,2 and 5) and(Lu_1-ySc_y)₂O₃:5 at%Eu(y=0,20 at%,50 at% and 70 at%) single crystals were grown by floating zone(FZ) method in air atmosphere.The structures of ...     

Synthesis,photoluminescence properties and thermal investigation by TG-MS of RE(DAS)_3·xH_2O(RE=Eu~(3+),Tb~(3+))

Rare earth(Ⅲ) diphenyl-4-amine sulfonates(RE(DAS)_3·xH_2O,RE=Eu~(3+),Tb~(3+))phosphors were synthesized by precursor method from barium diphenyl-4-amine sulfonate and rare earth sulfates.FTIR,TG/DSC coupled to mass spectrometry(TG/DSC/MS),X-ray powder diffraction(XPD),scanning electron microscopy(SEM) and photo luminesce nce(PL) spectroscopy were utilized to structurally and morphologically characterize the samples.Thermal decomposition of Eu(DAS)_3·7H_2O and Tb(DAS)_3·2H_2O at 973 K under dynamic air atmosphere results in crystalline Eu_2O_2SO_4 and Tb_2O_2SO_4 materials,respectively.Accordingly,MS spectra reveal the liberation of thermal decomposition products of precursors,largely as CO_2,NO_2 and SO_2 gases.The diphenyl-4-amine sulfonate(DAS) ligand demonstrats a good stabilizing property for Eu~(3+) and Tb~(3+) ions.The Eu(DAS)_3·7H_2O and Tb(DAS)_3·2H_2O compounds display efficient red and green emissions,under UV excitation,arising from the ~5D_0→~7F_J(J=0-4) and ~5D_4→~7F_J(J=0-6) transitions of the Eu~(3+) and Tb~(3+) ions,respectively.     

Zirconium metal organic framework for design of tetragonal rare earth-doped zirconia nanoparticles

Zirconium metal–organic frameworks ZrOBDC (where BDC = C₆H₄(COOH)₂, terephthalic acid) doped and co-doped with rare earth ions Ln (ZrOBDC:Ln³⁺, where Ln³⁺ = Eu³⁺ and Tb³⁺ as well as Er³⁺ and Yb³⁺) were used as precursors for the design of tetragonal rare earth doped zirconia nanoparticles (t-ZrO₂:Ln³⁺ NPs) through annealing process. Preparation, characterization and luminescence properties of ZrOBDC:Ln³⁺ and ZrO₂:Ln³⁺ NPs were investigated. The as-obtained t-ZrO₂:Ln³⁺ NPs have high purity with an average size of 20–30 nm. The luminescence spectra of ZrOBDC:Tb³⁺ and ZrOBDC:Eu³⁺ display strong green and red emission at around 544 and 611 nm which correspond to ⁵D₄ → ⁷F₅ and ⁵D₀ → ⁷F₂ transitions of Tb³⁺ and Eu³⁺ ions, respectively. The green and red up-conversion emissions of ZrO₂:Er³⁺,Yb³⁺ NPs due to ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions are observed under 976 nm laser excitation.     

Synthesis and luminescence properties of Tb3+/Eu3+ co-doped GdAlO3 phosphors with enhanced red emission

The(Gd_(0.97-x)Eu_xTb_(0.03))AIO_3(x= 0.005-0.07) phosphors were synthesized by the co-precipitation method,using ammonium bicarbonate as a precipitant.The combined technologies of FT-IR,XRD,FESEM,PLE/PL and photo luminescence decay analysis were used to study the phase evolution,morphologies and luminescent properties.The phosphors with good dispersion exhibit strong vivid red emission located at 617 nm(~5 D_0-~7 F_2 transition of Eu~(3+)) under the optimal excitation wavelength of 275 nm(~4 f~8-4 f~75 d~1 transition of Tb~(3+),~8 S_(7/2)→6~I_J transition of Gd~(3+)).The presence of Gd~(3+) and Tb~(3+) excitation bands on the PLE spectra monitoring the Eu~(3+) emission directly gives an evidence of Tb~(3+) → Eu~(3+) and Gd~(3+) → Eu~(~(3+)) energy transfer,The emission intensity varies with the Eu~(3+) amount,and the quenching concentration is ～5 at% which is close to the calculated value.The quenching mechanism is determined to be the exchange reaction between Eu~(3+).The temperature-dependent PL analysis indicates that the best(Gd_(0.92)Eu_(0.05)Tb_(0.03))AlO_3 sample possesses good thermally stable properties.All the(Gd_(0.97-x)Eu_xTb_(0.03))AIO_3 phosphors in this work have similar CIE chromaticity coordinates and color temperatures,which are(0.65 ± 0.02,0.35 ± 0.02) and ～2558 K,respectively.Fluorescence decay analysis shows that the lifetime for～617 nm emission decreases with the content of Eu~(3+) and temperature increasing.Owing to the Tb~(3+)→ Eu~(3+) energy transfer,the luminescent properties of the(Gd_(0.92)Eu_(0.05)Tb_(0.03))AlO_3 phosphors are superior to the single Eu~(~(3+)) doped sample(Gd_(0.95)Eu_(0.05))AlO_3.As a result,the prepared phosphors may be widely used in solid-state display and light emitting devices.     

Specific features of Eu^3＋ and Tb^3＋ magnetooptics in gadolinium-gallium garnet （Gd3Ga5O12）

We reported magnetooptical properties of Eu3+(4f(6)) and Tb3+(4f(8)) in single crystals of Gd3Ga5O12 (GGG), Y3Ga5O12 (YGG), and Eu3+(4f(6)) in Eu3Ga5O12 (EuGG) for both ions occupying sites of D2 symmetry in the garnet structure. Absorption, luminescence, and magnetic circular polarization of luminescence (MCPL) spectra of Tb3+ in GGG and YGG and absorption and magnetic circular dichroism (MCD) of Eu3+ in EuGG were studied. The data were obtained at 85 K and room temperature (RT). Magnetic susceptibility of Eu3+ in EuGG was also measured between 85 K and RT. The magnetooptical and magnetic susceptibility data were modeled using the wavefunctions of the crystal-field split energy (Stark) levels of Eu3+ and Tb3+ occupying D2 sites in the same garnets. The results reported gave a precise determination of these Stark level assignments and confirmed the symmetry labels (irreducible representations) of the closely-spaced Stark levels (quasi-doublets) found in the 5D1 (Eu3+) and 5D4 (Tb3+) multiplets. Ultraviolet (UV) excitation (<300 nm) of the 6PJ and 6IJ states of Gd3+ in the doped GGG crystals led to emission from 5D4 (Tb3+) and 5D1 and 5D0 (Eu3+) through radiationless energy transfer to the 4f(n-1)5d band of Tb3+ and to UV quintet states of Eu3+. The temperature-dependent emission line shapes and line shifts of the magnetooptical transitions excited by UV radiation suggested a novel way to explore energy transfer mechanisms in this rare-earth doped garnet system.     

Synthesis and optical characterization of Eu2+,Tb3+-codoped Sr3Y(PO4)3 green phosphors

A series of Eu~(2+),Tb~(3+)-codoped Sr_3 Y(PO_4)_3(SYP) green phosphors were synthesized by hightemperature solid-state reaction. Several techniques, such as X-ray diffraction, UV-vis spectrum,and photoluminescence spectrum, were used to investigate the obtained phosphors. The present study investigates in detail photoluminescence excitation and emission properties, energy transfer between the two dopants, and effects of doping ions on optical band gap. SYP:0.05 Eu2+ phosphor shows an intense and broad excitation band ranging from 220 to 400 nm and exhibits a bright green emission band with CIE chromaticity coordinates(0.189, 0.359) under 350 nm excitation. Green emission of SYP:0.03 Tb3+ is intensified by codoping with Eu~(2+), and energy transfer mechanism between them is demonstrated to be a dipole-dipole interaction. Upon 350 nm excitation, SYP:Eu~(2+),Tb~(3+) phosphors exhibits two dominating bands peaking at 466 and 545 nm, which are assigned to 4 f~65 d~1→4 f~7 transition of Eu~(2+) ions and ~5 D_4→~7 F_5 transition of Tb~(3+) ions, respectively. Optimal doping concentrations of Eu~(2+) and Tb~(3+) in the SYP host are 5 mol% and 15 mol%, respectively. Results indicate that SYP:Eu~(2+),Tb~(3+) phosphors are potentially used as green-emitting phosphors for white light-emitting diodes.