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+.     

Size dependence of up-conversion luminescence of NaYF₄:Yb³⁺/Tm³⁺

Tm3+/Yb3+ codoped NaYF4 microcrystals were synthesized using a hydrothermal method.The bright upconversion light was observed under 980 nm excitation.The upconversion luminescence was systematically investigated at different Yb3+ concentrations and different reaction temperatures and time.The sample with 60% Yb3+ concentration and reacting at 180 oC for 24 h possessed the highest luminescent efficiency.The higher luminescent efficiency was contributed to a large surface area.The large surface area induced the large vibration mode by absorbed H2O and CO2.The larger vibration mode could enhance the energy transfer efficiency from the excited Yb3+ to Tm3+ by the process of phonon assisted energy transfer.     

Controlled synthesis and tunable luminescence of NaYF₄:Eu³⁺

High quality NaYF4:Eu3+ luminescent materials were successfully synthesized via a facile template technique by hydrothermal method.The samples were characterized by X-ray powder diffraction(XRD),transmission electron microscopy(TEM) and fluorescence spectroscopy(FS).The incorporating of Eu3+ ions into NaYF4 crystal lattice influenced the symmetry types of NaYF4 crystals,resulting in phase transformation of NaYF4 crystals between α and β phase.The pure hexagonal phase of branched NaYF4:Eu3+ was obtained as the Eu3+ concentration reached 15 mol.%.In addition,the luminescence color was tuned by changing the doping concentration of Eu3+ ions.     

Intense blue-emitting Ca₂PO₄Cl:Eu²⁺ phosphor for near-ultraviolet converting white light-emitting diodes

A blue phosphor Ca2PO4Cl:Eu2+(CAP:Eu2+) was synthesized by solid state reaction.The Ca2PO4Cl:Eu2+ exhibited high quantum efficiency and excellent thermal stability.The luminescent intensity of Ca2PO4Cl:Eu2+ was found to be 128% under excitation at 380 nm,149% under 400 nm,and 247% under 420 nm as high as that of BaMgAl10O17:Eu2+.The optimal doping concentration was observed to 11 mol.% of CAP:Eu2+.The energy transfer between Eu2+ ions in CAP were occurred via electric multipolar interaction,and the critical transfer distance was estimated to be 1.26 nm.A mixture of blue-emitting Ca2PO4Cl:Eu2+,green-emitting(Ba,Sr)2SiO4:Eu2+ and red-emitting CaAlSiN3:Eu2+ phosphors were selected in conjunction with 400 nm chip to fabricate white LED devices.The average color-rendering index Ra and correlated color temperature(Tc) of the white LEDs were found to be 93.4 and 4590 K,respectively.The results indicated that it was a promising candidate as a blue-emitting phosphor for the near-UV white light-emitting diodes.     

Luminescent properties of Eu³⁺-doped BaZrO₃ phosphor for UV white light emitting diode

A novel orange phosphor Eu3+ doped barium zirconate(BaZrO3) was synthesized by conventional solid state reaction method and its crystal structure and luminescent properties were investigated in this paper.The X-ray diffraction patterns(XRD) showed that simple BaZrO3 phase was obtained.Monitoring at 596 nm,the excitation spectrum consisted of a broad band and a series of narrow bands and the stronger excitation peaks located at 275 and 393 nm,respectively.The emission spectrum excited by 393 nm UV light was composed of four narrow bands.The strongest emission was located at 596 nm.The appropriate concentration of Eu3+ was 0.025(molar fraction) for the highest emission intensity at 596 nm.The H3BO3 and ammonium were added as flux and the results showed that 2 wt.% NH4F ions was the optimal flux for BaZrO3:Eu3+.     

Energy transfer from Ce~(3+) to Tb~(3+) and Eu~(3+) in zinc phosphate glasses

Ce3+,Eu3+ and Tb3+ singly doped and Ce3+/Eu3+ and Ce3+/Tb3+ co-doped zinc phosphate glasses were prepared by sintering P2O5,ZnO,Ce2(C2O4)3·10H2O and Eu2O3/Tb4O7 mixtures at 1200 °C in the air for 2 h and then annealing at 450 °C for 10 h.The obtained glasses were homogeneous and transparent.The glasses without Ce3+ were colorless and those with Ce3+ showed slightly yellow.The singly doped glasses showed strong emissions and excitations from doped trivalent rare earth ions.Strong energy transfer from Ce3+ to Tb3+ was observed for Ce3+/Tb3+ coped samples.There were also some very weak evidences for the energy transfer from Ce3+ to Eu3+.     

Electrospinning synthesis and luminescent properties of Lu₂O₃:Eu³⁺ nanofibers

One-dimensional Lu2O3:Eu3+ nanofibers were prepared by electrospinning followed by high-temperature calcinations.Thermogravimetric and differential thermal analysis,X-ray powder diffraction,Fourier transform infrared spectroscopy,scanning electron microscopy,photoluminescent spectra and decay curves were used to characterize the samples.Results showed that samples began to crystallize at ～500 oC and crystallized completely around 1000 oC.The average diameter of nanofibers(1000 oC annealed) was about 55 nm and the particle size of Lu2O3:Eu3+ increased with increasing annealing temperature.Under ultraviolet excitation,nanofibers exhibited typical red emission of Eu3+ in Lu2O3.The effect of heat-treatment temperature on luminescent properties of nanofibers was also 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.     

Photoluminescence study of SiO₂ coated Eu³⁺:Y₂O₃ core-shells under high pressure

Uniform core-shell Eu3+:Y2O3/SiO2 spheres were synthesized via precipitation and the Stber method.The structural transition of core-shell Eu3+:Y2O3/SiO2 was studied by using high pressure photoluminescence spectra.With pressure increasing,the emission intensities of 5D0→7F0,1,2 transitions of Eu3+ ions decreased and the transition lines showed a red shift.The relative luminescence intensity ratio of 5D0→7F2 to 5D0→7F1 transitions decreased with increasing pressure,indicating lowering asymmetry around Eu3+ ions.During compression,structural transformation for cores in the present core-shell Eu3+:Y2O3/SiO2 sample from cubic to monoclinic took place at 7.5 GPa,and then the monoclinic structure turned into hexagonal above 15.2 GPa.After the pressure was released,the hexagonal structure transformed back to monoclinic and the monoclinic structure was kept stable to ambient pressure.     

Cooperative energy transfer in Eu3+,Yb3+ codoped Y2O3 phosphor

Under 980 nm laser excitation,red emission(5D0-7FJ(J=0,1,2)) of Eu3+ was observed in cubic Y2O3 codoped with Eu3+ and Yb3+.The dependence of the upconverted emission on doping concentration and laser power was studied.Yb3+ emission around 1000 nm(2F5/2-2F7/2) was reported upon excitation of Eu3+ ions.The decay curves of 5DJ(J=0,2) emission of Eu3+ under excitation of 266 nm pulse laser were examined to investigate the Eu3+→Yb3+ energy transfer process.Cooperative energy transfer process was discussed as the possible mechanism for the visible up-conversion luminescence of Eu3+ and near-infrared down-conversion emission of Yb3+.     

Pressure effect on optical properties and structure stability of LaPO₄:Eu³⁺ hollow spheres

Uniform monoclinic monazite structure LaPO4:Eu3+ hollow spheres were s ynthesized via an attractive hydrothermal method owing to the higher yield and s implicity.Photoluminescence and Raman spectra of the sample were investigated u nder high pressure up to 26 GPa using diamond anvil cells.At ambient pressure,the sample exhibited same luminescent properties with that of bulk monazite LaPO 4:Eu3+.With the increase of pressure,the emission intensity of Eu3+ decreased and the half-widths of transition lines increased,while emission peaks showed a red shift toward longer wavelengths due to increase in crystal-field strength.No phase transformation appeared before amorphization for monoclinic LaPO4:Eu3+ hollow spheres,which was confirmed based on the analysis of high pressure Raman spectra.The large surface energy of hollow spheres was proposed to prevent the occurrence of phase transformation.     

Effects of Sr²⁺ on structure and luminescent properties of BaAl₁₂O₁₉:Eu phosphors

Ba0.9-ySryAl12O19:Eu0.1 phosphors were prepared by sol-gel technique,the crystalline structures of samples characterized by XRD,and the luminescence properties were investigated.The influence of crystallographic positions on the luminescent properties of Sr2+-doped BaAl12O19:Eu was investigated in detail.The results indicated that the crystal lattice of BaAl12O19:Eu was not influenced by the Sr2+ and doping Sr2+ in BaAl12O19:Eu enhanced the luminescent properties of the phosphors at the proper concentration of Sr2+.With the increasing of concentration of Sr2+ doped in BaAl12O19:Eu,the relative luminescent intensity of Ba0.9-ySryAl12O19:Eu0.1 strengthened and blue-shifted.     

Effects of aluminum co-doping on photoluminescence properties of Ce³⁺-doped SiO₂ glasses

SiO2 glasses co-doped with Al3+ ions were prepared by a sol-gel method by holding 0.5% of Ce3+ ions constant and varying the Al3+ ions concentrations.Thermal stability,the structural,chemical and the optical properties of the samples were studied by using differential scanning calorimetric(DSC),thermo gravimetric analysis(TGA),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),UV-vis spectroscopy and photoluminescence spectroscopy(PL).The DSC and TGA of samples depicted that the presence of dopant and co-dopant decreased the endothermic peak temperature and the yield respectively.SEM images showed that the particles were in the nano-range and spherical in shape.The XRD showed that all the samples were amorphous.The UV absorption measurements indicated that the presence of Al3+ ions significantly reduced the SiO2 absorption band,increased the absorbance intensity of SiO2 and decreased the transmittance as compared to the presence of the Ce3+ ions alone.The photoluminescence results displayed an optimum increase in luminescence intensity when the ratio of Al:Ce was 10:1 and further increase in aluminum content quenched the luminous intensity.     

Optimization of BaMgAl₁₀O₁₇:Eu²⁺ phosphors by the substitution of Si-N bonds for Al-O bonds

We proposed a simple method to improve the thermal stability of BaMgAl10O17:Eu2+(BAM) phosphors by the substitution of Si-N bonds for Al-O bonds in the host lattice.Both photoluminescence properties and thermal stability under ultraviolet(UV) and vacuum ultraviolet(VUV) excitation could be significantly improved through Si-N incorporation.After thermal degradation at 600 °C for 1 h in air atmosphere,the Si-N doped sample(Ba0.88Eu0.12MgAl9.97Si0.03O16.97N0.03) had the highest emission intensity which was 22% and 40% stronger than that of as-received sample under UV and VUV excitation,respectively.This could be attributed to the stable local structure surrounding the Eu2+ ions and the lower electronegativity of nitrogen.     

Energy transfer between Gd^3＋ and Tb^3＋ in phosphate glass

The phosphate glass doped with Gd3+,Tb3+ and Gd3+/Tb3+ were prepared by high temperature melting.The photo-luminescence behavior of Gd3+ and Tb3+ in phosphate glass were investigated by absorption,excitation,and emission spectroscopy.Energy transfer between Gd3+ and Tb3+ in phosphate glass was studied,and it was found that there were two energy transfer mechanisms between Gd3+ and Tb3+ in phosphate glass: one was from 4f7 level of Gd3+ to the 4f8 level of Tb3+,and the other was from 5d level of Tb3+ to 4f7 level of Gd3+.The new findings would be beneficial for the study of Tb3+-doped scintillating phosphate glass.     

Long Lasting Phosphorescence in Eu2+ and Ce3+ Co-Doped Strontium Borate Glasses

Long lasting phosphorescence (LLP) was observed in Eu2+, Ce3+ co-doped strontium borate glasses prepared under the reducing atmosphere due to the emission of both Eu2+ and Ce3+. The methods of photoluminescence, thermoluminescence and phosphorescence were used to study the samples, and possible mechanism was suggested. The co-doping of Ce3+ ions poisoned the phosphorescence emission of Eu2+ because of the competition to obtain the trapped electron. The phosphorescence of Ce3+ in the sample decays more quickly than that of Eu2+, which is suggested for the reason that the emission energy of Ce3+ is higher or the distance between Ce3+ and electron traps of the glasses is longer.     

Simulation of f-d transition using the extended crystal-field model:parameter dependent study for Er³⁺ in various hosts

The 4f-5d transitions of Er3+ ions doped in crystals were widely studi ed due to their potential applications in quantum cutting phosphors and VUV lase rs,etc.The theory to do the calculations of 4f-5d transitions and various rela ted aspects,such as the ways to determining various parameters,were summarized .The impacts of various interactions on the spectra were also demonstrated clea rly with Er3+ ions in crystals CaF2 and LiYF4.Predicted results were compared w ith measured spectra.     

Studies on synthesis and fluorescent property of rare earth complexes RE（ABMF）2AA and copolymers RE（ABMF）2AA-co-MMA

Four new complexes RE(ABMF)2AA (RE=Sm, Eu, Tb, Dy) were synthesized by the reaction of RECl3·6H2O with acrylic acid (HAA) and 1-(2-furyl)-3-phenyl-1,3-propanedione (ABMF). The copolymerization of the rare earth complexes with methyl methacrylate was studied by using 2,2-azobis-isobutyronitrile as an initiator. The composition and structure of the four complexes were characterized by elemental analysis, UV-vis and FTIR. The glass transition temperature and molecular weight of the copolymers were determined. Photoluminescent measurement showed that ligand ABMF could efficiently transfer the energy to Sm3+ and Eu3+ ions in the complexes and sensitize the luminescence of the rare earth ions, but could not sensitize Tb3+ and Dy3+ ions. As a result, both Sm3+ and Eu3+ complexes emitted the characteristic fluorescence of Sm3+ and Eu3+ ions due to the f-f transitions. The four copolymers could emit strong fluorescence of the rare earth ions.     

Energy transfer in Tb~（3＋）,Yb~（3＋） codoped Lu_2O_3 near-infrared downconversion nanophosphors

Tb3+ and Yb3+ codoped Lu2O3 nanophosphors were synthesized by the reverse-strike co-precipitation method. The obtained Lu2O3:Tb3+,Yb3+ nanophosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectra. The XRD results showed that all the prepared nanophosphors could be readily indexed to pure cubic phase of Lu2O3 and indicated good crystallinity. The Tb3+→Yb3+ energy transfer mechanisms in the UV-blue region in Lu2O3 nanophosphors were investigated. The experimental results showed that the strong visible emission around 543 nm from Tb3+ (5D4→7F5) and near-infrared (NIR) emission around 973 nm from Yb3+ (2F5/2→2F7/2) of Lu2O3:Tb3+,Yb3+ nanophosphors were observed under ultraviolet light excitation, respectively. Tb3+ could be effectively excited up to its 4f75d1 state and relaxed down to the 5D4 level, from which the energy was transferred cooperatively to two neighboring Yb3+. The Yb3+ concentration dependent luminescent properties and lifetimes of both the visible and NIR emissions were also studied. The lifetime of the visible emission decreased with the increase of Yb3+ concentration, verifying the efficient energy transfer from the Tb3+ to the Yb3+. Cooperative energy transfer (CET) from Tb3+ to Yb3+ was discussed as a possible mechanism for the near-infrared emission. When doped concentrations were 1 mol.% Tb3+ and 2 mol.% Yb3+, the intensity of NIR emission was the strongest.     

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.