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 studied due to their potential applications in quantum cutting phosphors and VUV lasers, etc. The theory to do the calculations of 4f-5d transitions and various related aspects, such as the ways to determining various parameters, were summarized. The impacts of various interactions on the spectra were also demonstrated clearly with Er³⁺ ions in crystals CaF₂ and LiYF₄. Predicted results were compared with measured spectra.     

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.     

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.     

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.     

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+.     

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.     

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.     

Synthesis of well oil-dispersible BaYF₅:Yb³⁺/Er³⁺ nanocrystals with green upconversion fluorescence

Nearly monodisperse,regular-shaped and well oil-dispersible tetragonal BaYF5:0.2Yb3+/0.02Er3+ nanocrystals(NCs) were synthesized in water-ethanol-oleic acid-sodium oleate system.The as-obtained NCs exhibited bright upconversion(UC) fluorescence under the 980 nm excitation.Blue(2H9/2-4I15/2),green((2H11/2,4S3/2)-4I15/2) and red(4F9/2-4I15/2) transitions were observed.The results indicated that the relative intensity of green to red increased gradually with increasing power density,which were seldom in the previous work.Therefore,the UC properties and mechanism were studied in detail.     

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.     

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.     

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+.     

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.     

Synthesis and characterization of CaAl_xO_y:Eu²⁺ phosphors prepared using solution-combustion method

Europium-doped calcium aluminate(CaAlxOy:Eu2+) phosphors were obtained at low temperatures(500 oC) by the solution-combustion of corresponding metal nitrate-urea solution mixtures.The particle size and morphology and the structural and luminescent properties of the as-synthesized phosphors were examined by means of scanning electron microscopy(SEM),X-ray diffraction(XRD),Auger spectroscopy,transmission electron spectroscopy(TEM) and photoluminescence(PL).It was found that the Ca:Al molar ratios showed greatly influence not only on the particle size and morphology,but also on their PL spectra and structure.With the Ca:Al molar ratios increasing from 6:100 to 26:100,the structure of as-synthesized phosphor changed from CaAl12O19 to monoclinic CaAl2O4 and the dominant emitting light from red to blue,implying that the oxidation state of doped europium ions changed from trivalent to divalent due to the structure variation of host lattice.A blue phosphor with almost pure phase can be easily prepared by solution combustion method with suitable Ca:Al molar ratio.     

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.     

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.     

Synthesis and characterization of YAG:Ce³⁺ fluorescence powders by co-precipitation method

YAG:Ce3+(Yttrium aluminum garnet) fluorescence powders were successfully prepared by co-precipitation method using aluminum nitrate,yttrium nitrate,cerous nitrate as the starting materials and ammonium carbonate as precipitant.The products were characterized by X-ray powder diffraction,luminescence spectrometer,transmission electron microscope(TEM).The XRD results showed that the obtained YAG:Ce3+ fluorescence powders had the crystalline structures of YAG at calcinations temperature of 900 oC and the TEM results showed that the grain diameters were about 100 nm.The YAG:Ce3+ fluorescence powders,synthesized by co-precipitation method,had the best luminescence property when the Ce doping amount was x=0.06 in the molecular formula of Y3-xCexAl5O12,the calcinations time was 2 h and the calcinations temperature was 1000 °C.     

Study on analysis of crystal structure in CeO₂ doped with Er₂O₃ or Gd₂O₃

To simulate the effects of burnable poison doping in nuclear fuel UO2,Er2O3(or Gd2O3)-doped CeO2 pellets were prepared. Changes in lattice constant and atomic disordering for CeO2 due to the Er2O3 and Gd2O3 doping were measured by means of XRD and XAFS. By the Er2O3 doping,the lattice constant decreased,and a disordering of lattice structure was induced in the samples. The doping with Er2O3 also induced the disordering of atomic arrangement around Er atoms,which was observed through the change in XAFS spectra. In contrast,the effect of Gd2O3 doping was smaller than that of Er2O3 doping. The result was discussed in terms of ionic size of dopants in CeO2 crystal.     

Facile synthesis of visible light excited La_1-xGd_xF₃:Eu³⁺ micro-meter sphere using polyvinylpyrrolidone as a template

Lanthanide fluorides exhibited unique luminescent properties in terms of their low phonon energy can restrict the luminescence quenching and extend luminescent lifetimes.Here,a room-temperature co-precipitation method was used to synthesize europium(III) activated La1-xGdxF3 solid phosphors.X-ray diffraction(XRD) data confirmed the crystalline phases of synthesized sample belongs to orthorhombic system.All the as-derived materials exhibited red luminescence(5D0→7F1) under the excitation at longer wavelengths(394 and 466 nm).The powder with the most intense emission was achieved in terms of 10 mol.% doping concentration(Eu content,La/Gd=1/9) and sample sintered at 700 oC.Scanning electron microscopy(SEM) investigated the morphology and crystalline of the samples,showing that many regular and large balls(5-10 μmol/L) were dispersed within the micro-meter scale composites.We proved that the above crystal growth structures were controllable and predicable based on the surface functionalization by polyvinylpyrrolidone ligand.