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.     

Polarized spectral analysis of Er3+ ions in Er3+/yb3+:LiLa(MoO4)2 crystal

Optical characteristics and upconversion dynamics of Er3+ in Er3+/Yb3+:LiLa(MoO4)2 crystals were investigated. The absorption spectra, fluorescence spectra and the fluorescence decay curves were analyzed at room temperature. The infrared emission at 1538 nm and visible emissions at 520–569 and 640–670 nm, corresponding to 2H11/2,4S3/2→4I15/2 and 4F9/2→4I15/2 transitions of Er3+ ions, were simultaneously observed in Er3+/Yb3+:LiLa(MoO4)2 crystals under 976 nm excitation at room temperature. The maximal emission cross-section near 1530 nm for π-polarization was 0.63×10–20 cm2 and the measured lifetime of 4I13/2 was 4.88 ms. The upconversion process was involved in sequential two-phonon processes, either the energy transfer from Yb3+ ions or by the excited state absorption.     

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.     

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.     

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.     

Enhancement of 1.54 μm emission in Er：LiNbO_3 crystal by codoping with Zn~（2＋） ions

The enhanced intensity and lengthened lifetime of 1.54 μm emission were observed for Er:LiNbO3 crystal codoped with Zn2+ ions.The ZnO codoping led to the reduction of the green upconversion emission in Er:LiNbO3 crystals.The decay trace of the 4S3/2→4I15/2 was ob-viously nonexponential for Er:LiNbO3 codoped with 0 and 3 mol.% ZnO,but became exponential for one codoped with 6 mol.% ZnO.The OH-absorption spectra showed after codoping with Zn2+ ions,the OH-absorption peaking position shifted from ~3495 to 3484 cm-1,and the absorption cross section decreased.These spectroscopic characteristics suggested that the improvement of 1.54 μm emission was attributed to the reduction of Er3+ cluster sites.     

Magnetic and XPS studies of lithium lanthanide tetraphosphates LiLnP4O12 （Ln=Nd, Gd, Er）

Magnetic susceptibilities of flux-grown single crystals of LiLnP4O12 (Ln=Nd,Gd, Er) were measured in the temperature range of 2-300 K. The compounds were paramagnetic, and obeyed the Curie-Weiss law in the entire temperature interval, without magnetic phase transitions, and with effective magnetic moments close to those of the corresponding free Ln3+ ions. X-ray photoelectron spectroscopy was applied to determine the positions of core-level electrons relative to the Fermi level: Li 1s; Ln 4f, 5p, 5s, 4d, 3d; P 2s, 2p; O 1s, 2s. The binding energies in these compounds were found slightly shifted compared to the respective values of the same elements.     

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.     

Growth and Optical Spectra of Zn:Er:LiNbO3 Crystals Using Bridgman Method

The growth of LiNbO3 single crystal with Er3 and Zn2 co-doped using Bridgman method and its characteristicabsorption spectra and fluorescence spectra were reported. Large-size crystals initially containing Zn2 (3%) and Er3 diffraction and differential thermal analysis (DTA) were used to characterize the crystals. The results indicate that the con-centration of Er3 ions in crystals, their absorption intensity, and their fluorescence intensity decrease from the bottom to thetop in the crystals. However, for the upper part of the crystal, the up-conversion fluorescence intensity is higher than that ofthe lower part excited by an 800 or 970 nm pump. The effects of the crystal lattice, their structural defect and their effectivesegregation of Er3 ions were discussed with respect to the variations of the up-conversion fluorescence intensity.     

Interpretation of the 4f-5d Excitation Spectra of Eu^3＋ and Tb^3＋ Doped in Crystals

The structure of the low-temperature 4f^N→4f^N-15d excitation spectra of Eu^3＋ and Tb^3＋ doped in crystals LiYF4, YPO4 and CaF2 measured by van Pieterson et al. in 2002 was analyzed and assigned based on the simple model proposed by Duan and co-workers in the last few years. Some complemental discussion on effects of J-mixing on the f-d transition intensities for Eu^3＋ due to the f-electron crystal-field interaction Hcf（f）, which was ignored in the simple mod- el, was presented. Some previously unexplained peaks for Tb^3 ＋ were interpreted to be spin-forbidden transitions to higher 5d crystal-field levels, or assigned to be f→d excitations with the core 4f7 excited from ^8S to ^6P, ^6I and ^6D, respectively. It is shown that the main structure of 4f-Sd excitation spectra of Eu^3＋ and Tb^3＋ can be well interpreted with the simple model.     

Energy transfer and frequency upconversion in Er~（3＋）-Yb~（3＋） codoped oxy-fluoro-tungstosilicate glasses

Er3+-Yb3+ codoped oxy-fluoro-tungstosilicate glasses with infrared-to-visible frequency upconversion luminescence were prepared by melting quenching in air.The effects of Er3+ doping on the optical properties of the samples were measured by means of techniques such as optical absorption spectra and photoluminescence spectra.The results showed that intense green and red signals centered at 546 and 665 nm,corresponding to the 4S3/2 → 4I15/2 and 4F9/2 → 4I15/2 transitions of Er3+ by a multiphoton stepwise phonon-assisted excited-state absorption process,respectively,were simultaneously observed by exciting the samples with a diode laser operating at 980 nm at room temperature.The upconversion process was found very sensitive to Er3+ content at a constant Yb2O3 content of 5 mol.%.With the increase of Er3+ content from 0.5% to 1.5%,the upconversion intensity increased gradually.Further increasing of Er3+ content to 3.0% resulted in a significant fluorescence quenching.Moreover,the possible upconversion mechanisms were discussed based on the energy-matching conditions and the quadratic dependence on excitation power.     

Up-Conversion Emission of Er3+ Ions in Yb3+ Sensitized Oxide Crystals

Most of the up-conversion lasers operated at room temperature are realized with heavy metal fluorides, In this paper the Judd-Ofelt parameters Ωλ ( λ = 2,4,6 ) were calculated for Er3+ ions in Yb3 + sensitized LiNbO3 and YVO4 crystals at room temperature, together with the radiative transition probabilities, non-radiative transition probabilities and resonant transition probabilities of Er3+ ions. Taking into account the energy transfer from Yb3 + to Er3 +, the rate equations are given for Er3 + ions. We obtained from a solution of the rate equations that Yb3 + sensitized YVO4 crystal is more efficient than Yb3 + sensitized LiNbO3 crystal in the up-conversion of 550 nm of Er3+ emission, which is consistent with our observation.     

Investigation on energy transfer from Er3+ to Nd3+ in teilurite glass

A study of energy transfer of Er3+/Nd3+ codoped tellurite glasses was presented. By Nd3+ co-doping, both the Er3+ green emission corresponding to the Er3+: (4S3/2,2H11/2)→4I15/2 transitions and the red emission corresponding to the Er3+: 4F9/2→4I15/2 transitions were quenched. The energy transfer mechanism between Er3+ and Nd3+ was discussed based on their energy level characteristics. The interaction parameters, CD-A, for the energy transfer processes from Er3+ to Nd3+ in tellurites glass were calculated. Finally, the resonant transfer Er3+: 4I9/2→Nd3+: (4F5/2, 2H9/2) was proposed to be the most probable microscopic process to occur in contrast with the other processes.     

Up-conversion luminescence from Nd~(3+) ions doped in NaBi(WO_4)_2 single crystal

The luminescence of Nd3+-doped in NaBi(WO4)2 single crystal was investigated from 10 K to room temperature.The excitation source was a pulsed dye laser in resonance into the(4G5/2+2G(1)7/2) levels of Nd3+ ions.Several blue emission bands in the up-conversion luminescence spectra corresponded to transitions from 2P1/2 to 4I9/2.Some violet bands corresponding to transitions of 4D3/2→(4I9/2,4I11/2,4I13/2) were also observed.For comparison,the luminescence spectra and decay curves excited by the pulsed 355 nm l...     

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.     

Local microstructure and photoluminescence of Er-doped 12CaO·7Al2O3 powder

Er-doped 12Ca0.7Al2O3 （C12A7：Er） powders were prepared using the sol-gel method followed by annealing inorganic precursors. X-ray diffraction （XRD）, Raman and absorption spectra revealed that Er ions existed and substituted Ca^2＋ lattice site in C12A7. The photoluminescence of C12A7：Er at room temperature was observed in the visible and infrared region using 488 nm （2.54 eV） Ar^＋ line as excitation source, respectively. The sharp and intense green emission bands with multi-peaks around 520 nm and 550 nm correspond to the transitions from the excited states ^2H11/2 and ^4S3/2 tO the ground state ^4I15/2, respectively. Furthermore, red emission band around 650 nm was also observed. It was attributed to the electronic transition from excited states ^4F9/2 to the ground state ^4I15/2 inside 4f-shell of Er^3＋ ions. The intensive infrared emission at 1.54 μm was attributed to the transition from the fast excited states of ^4I13/2 to the ground state （^4I15/2）. The temperature dependent photoluminescence of infrared emission showed that the integrated intensity reached a maximum value at near room temperature. The forbidden transitions of intra-4f shell electrons in free Er^3＋ ions were allowed in C12A7 owing to lack of the inversion symmetry in the Er^3＋ position in C12A7 crystal field. Our results suggested that C12A7：Er was a candidate for applications in Er-doped laser materials, and full color display.     

Local microstructure and photoluminescence of Er-doped 12CaO·7Al2O3 powder

Er-doped 12CaO·7Al2O3 (C12A7:Er) powders were prepared using the sol-gel method followed by annealing inorganic precursors. X-ray diffraction (XRD), Raman and absorption spectra revealed that Er ions existed and substituted Ca2 lattice site in C12A7. The photoluminescence of C12A7:Er at room temperature was observed in the visible and infrared region using 488 nm (2.54 eV) Ar line as excitation source, respectively. The sharp and intense green emission bands with multi-peaks around 520 nm and 550 nm correspond to the transitions from the excited states 2H11/2 and 4S3/2 to the ground state 4I15/2, respectively. Furthermore, red emission band around 650 nm was also observed. It was attributed to the electronic transition from excited states 4F9/2 to the ground state 4I15/2 inside 4f-shell of Er3 ions. The intensive infrared emission at 1.54μm was attributed to the transition from the first excited states of 4I13/2 to the ground state (4I15/2). The temperature dependent photoluminescence of infrared emission showed that the integrated intensity reached a maximum value at near room temperature. The forbidden transitions of intra-4f shell electrons in free Er3 ions were allowed in C12A7 owing to lack of the inversion symmetry in the Er3 position in C12A7 crystal field. Our results suggested that C12A7:Er was a candidate for applications in Er-doped laser materials, and full color display.     

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.     

Spectroscopic study of the Pr-doped BiBO glass and Ca4GdO（BO3）3 single crystals

Detailed spectroscopic studies of Pr³⁺ ions in BiBO glass and Ca₄GdO(BO₃)₃ crystal were performed. Experimental absorption spectra were measured at room temperature and assigned. The first principles discrete variational multielectron method was used to model the polarized absorption spectra of the Ca₄GdO(BO₃)₃:Pr³⁺; without any fitting parameters, the overall appearance of the spectra was reproduced satisfactorily. The energy intervals between different molecular orbitals in the [PrO₆] cluster were estimated. The conventional Judd-Ofelt theory was used to calculate the oscillator strengths of the 4f-4f transitions in the BiBO:Pr³⁺ system; the set of the phenomenological intensity parameters was determined.     

Influence of B2O3 on Spectroscopic Properties of Er^3＋/Yb^3＋ Co-Doped Tungsten-Tellurite Glasses

A series of novel Er^3＋/Yb^3＋ co-doped （85- x ） TeO2-15WO3-xB2O3 （TWB;x=2%,5%,8%（mole fraction） ） glasses were prepared. Influence of B203 on the spectroscopic properties of Er^3＋/Yb^3＋ co-doped tungsten-tellurite glasses were investigated. It is found that the intensity of 1.5μm fluorescence, lifetime of the ^4I13/2 level and upconversion fluorescence all decrease with the increase of B2O3 content. The product of full width at half maximum （FWHM） and stimulated emission cross-section （σe^peak） of Er^3＋ ：^4I13/2→^4I15/2 transition has an optimum when B203 is 5% （mole fraction）. The emission spectra of Er^3＋ ： ^4I13/2→^4I15/2 transition was analyzed using peak-fit routine, and an equivalent four-level system was proposed to estimate the stark splitting for the 411512 and ^4I13/2 levels of Er^3＋ ions in TWB glasses at room temperature.