Energy transfer processes from Yb3＋ to Ln3＋ （Ln=Er or Tm） in heavy metal glasses

Heavy metal glasses doubly doped with Yb3+ and Ln3+ ions(Ln=Er or Tm) were studied. Glass host matrices were limited to lead borate glass and lead germanate glass. Efficient resonant(Yb3+-Er3+) and non-resonant(Yb3+-Tm3+) energy transfer was observed for the studied systems. Near-infrared luminescence spectra at 1.53 μm(Er3+) and 1.9 μm(Tm3+) were detected under excitation of Yb3+ by 975 nm diode laser line. They corresponded to 4I13/2→4I15/2(Er3+) and 3F4→3H6(Tm3+) transitions of rare earth ions, respectively. The unusual large spectral linewidth nearly close to 110 nm for 4I13/2→4I15/2 transition of Er3+ ions in lead borate glass was obtained, whereas long-lived near-infrared luminescence at 1.53 μm was detected in lead germanate glass. Quite different situation was observed for Yb3+-Tm3+ doubly doped glasses. In contrast to lead borate glass, near-infrared(3F4→3H6) luminescence spectra were registered for Tm3+ ions in lead germanate glasses, only. These phenomena strongly depended on stretching vibrations of glass host, which was confirmed by FT-IR spectroscopy.     

Up-conversion luminescence properties of Yb^3＋ and Ho^3＋ co-doped Bi3.84W0.16O6.24 powder synthesized by hydrothermal method

Using polyethylene glycol (PEG) as the surfactant, Bi3.84W0.16O6.24 up-conversion luminescence nano-crystal co-doped with Yb3+ and Ho3+ ions was synthesized by the hydrothermal method. The structure and properties of luminescence powder were studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). It was of cubic system when the sample was synthesized at a low temperature and the particle size was about 30 nm. The results showed that adding surfactants was useful to improve the powder agglomeration and the grain crystal was spherical. The green emission peak at 546 nm and red emission peak at 655 nm, corresponding to the ( 5F4, 5S2)→ 5 I 8 and the 5 F 5 → 5 I 8 transitions of Ho 3+ , respectively, were simultaneously observed at room temperature under excitation of 980 nm semiconductor laser. The up-conversion luminescence intensity was the strongest when the concentration ratio of Yb3+ /Ho3+ was 6:1 and the concentration of Ho 3+ ion was 1.5 mol.%. The up-conversion mechanism was also studied. The green and red emission peaks were the two-photon absorption according to the relationship between the pump power and the luminescence intensity.     

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.     

Y4GeO8:Er3+,Yb3+ up-conversion phosphors for optical temperature sensor based on FIR technique

Herein, we reported novel Y₄GeO₈:Er³⁺,Yb³⁺ phosphors elaborated via conventional solid-state reaction, and we further explored their properties as optical thermometer by using fluorescence intensity ratio (FIR) method complemented by detailed analysis on crystal structure, up-conversion luminescence and energy transfer from Yb³⁺ to Er³⁺. Upon 980 nm laser excitation, Y₄GeO₈:Er³⁺,Yb³⁺ phosphors present 525, 547 and 659 nm emission bands assigned to the characteristic transitions of Er³⁺. Furthermore, Y₄GeO₈:Er³⁺,Yb³⁺ samples show outstanding temperature sensing performances. To be specific, the minimal temperature resolution is 0.03 K (303 K), and the relative sensitivity of FIR can be up to 1.152%/K (303 K). Hence, Y₄GeO₈:Er³⁺,Yb³⁺ phosphors can be possible candidates for thermometry devices.     

Design and achieving of multicolor upconversion emission based on rare-earth doped tellurite glasses

yD3＋/Tm3＋ co-doped and yD3＋/Ho3＋/Tm3＋ tri-doped tellurite glasses were synthesized by fusing the mixture of TeO2, PbF2, AIF3, BaF2, Yb2O3, Tm203 and H0203 in a cortmdum crucible at 850 ℃ for 20 min. The synthesized glasses were characterized by upconversion emission spectra under the excitation of 980 nm laser, and the emission colors were investigated according to the CIE-1931 standards. The results indicated that yD3＋/Tm3＋ co-doped tellurite glass exhibited blue upconversion emission with favor- able color coordinates of （0.20, 0.07）. Yb3＋, HO3＋ and Tm3＋ tri-doped tellurite glasses presented white upconversion luminescence under a single 980 nm laser excitation. Moreover, a very wide range of emission colors could be tuned by altering Ho3＋ concentration. Combining the contribution of adjusting Ho3＋ concentration and pump power, near equal energy white light was obtained.     

Preparation and upconversion luminescence of monodisperse Gd2O3：Ho^3＋,Yb^3＋ nanocrystals

Gd2O3:Ho3+,Yb3+ nanocrystals were synthesized via solvothermal method.X-ray diffraction(XRD),transmission electron microscopy(TEM),absorption and upconversion spectra were employed to characterize the synthesized nanocrystals.The results of XRD and TEM showed that obtained Gd2O3:Ho3+,Yb3+ nanocrystals were cubic in crystal structure and uniform spherical in morphology.The average crystallite size was calculated to be 7.5 nm.Green and red up-conversion emissions corresponding to(5F4,5S2)→5I8 and 5F5 → 5I8 transition were observed upon 980 nm excitation at room temperature.The results indicated that both green and red luminescence were based on the two-photon processes.Laser power and doping concentration dependence of the upconverted emissions were studied to understand the upconversion mechanisms.Excited state absorption and energy-transfer processes were discussed as the possible mechanisms for the visible emissions.     

Preparation and luminescence properties of BaWO4：yb3＋/Tm3＋ nano-crystal

This research investigated the effect of different contents of Tm3+and different concentration ratios of Yb/Tm on the lumi-nescent properties of BaWO4:Yb3+/Tm3+nano-crystal synthesized by the hydrother...     

Upconversion emission of SrYbF5：Er3＋nanosheets modified by Tm3＋ions

Through a hydrothermal route, the Er3＋and Tm3＋co-doped SrYbF5 nanosheets were synthesized. The resulting samples were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and luminescence spec-tra. Under the excitation of 980 nm laser irradiation, the upconversion emissions of Tm3＋ions centered at 474 nm （1G4→3H6）, 679 nm （3F2→3H6）, 699 nm （3F3→3H6）, 803 nm （3H4→3H6） and emissions of Er3＋ions centered at 522 nm （2H11/2→4I15/2）, 543 nm （4S3/2→4I15/2）, 654 nm （4F9/2→4I15/2） were observed. The upconversion emissions of Er3＋ions were adjusted by the concentration of Tm3＋ions. The energy transfer mechanisms among Er3＋-Yb3＋-Tm3＋in SrYbF5 nanosheets were discussed.     

Improving luminescence and thermometric performance of Ba2CaWO6:Er3+ by tri-doping with Yb3+ and Na+

The Er³⁺doped double perovskite Ba₂ CaWO₆ crystal is a promising ratiometric thermometer based on the fluorescence intensity ratio(FIR) of transitions from ² H_11/2 and ⁴ S_3/2to the lowered ⁴ I_15/2 level.However,the Ca²⁺vacancy defect caused by the charge difference between rare-earth ions and the substituted alkaline-earth ions gives rise to the non-radiative probability and limits the t...     

Multicolor luminescence of hexagonal NaYF4:Yb3+/Ho3+/Ce3+ microcrystals with tunable morphology under 940 nm excitation for temperature-responsive anti-counterfeiting

In this study, the hexagonal NaYF₄:Yb³⁺/Ho³⁺/Ce³⁺ microcrystals were synthesized controllably, and upconversion luminescence excited at 940 nm and its application in temperature-responsive anti-counterfeiting are reported. It is clarified that the Ln³⁺ (Ln = Y + Yb + Ho + Ce) density ratio of bottom plane to side plane in the unit cell can be regulated by Ce³⁺ doping. It is also proved that the energy transfer of Yb³⁺ to Ho³⁺ is responsible for the activation of Ho³⁺ under 940 nm excitation, while the cross relaxation between Ho³⁺ and Ce³⁺ participates in the redistribution of electron population of ⁵S₂/⁵F₄ and ⁵F₅ levels. Both theory and experiment confirm that the intensity ratio of red to green emission (I_R/I_G) as a function of temperature as an independent variable has good linear characteristics in the temperature range of 300–500 K. Due to the good responsiveness of multicolor luminescence to temperature, the hexagonal NaYF₄:Yb³⁺/Ho³⁺/Ce³⁺ with tunable morphology is a promising candidate for advanced temperature-responsive upconversion anti-counterfeiting. Our results provide a new pathway for the controllable synthesis of hexagonal NaYF₄ microcrystals as well as the regulation of upconversion luminescence that is excited by wavelengths other than 980 nm and its application in anti-counterfeiting.     

Luminescence properties of calcium tungstate activated by lanthanide(Ⅲ) ions

Calcium tungstate phosphors activated by the Ln3+ ions(Ln=Pr, Nd, Tb, Yb) were synthesized by a traditional high-temperature solid-state method. The crystal structures and morphologies of the products were characterized by scanning electron microscopy(SEM), X-ray powders diffraction(XRD) and infrared spectra(FT-IR). The samples were found to show luminescence properties(down-conversion, DC, at excitation wavelength 254 nm and up-conversion, UC, at excitation wavelength 980 nm). CaWO4 doped with Tb3+/Yb3+ showed green DC and UC luminescence characteristic of Tb(III) ion in the range of 470–660 nm, corresponding to the 5D4→7F6,5,4,3,2 electronic transition. CaWO4 doped with Pr3+/Yb3+ showed week blue, green and red(DC and UC) luminescence of Pr(III) ion, in the wavelength region of 450–700 nm. Emission peaks were ascribed to the 3P1→3H4,5,6, 3P0→3H4,5,6, 3P1→3F2 and 3P0→3F2 transitions, respectively. CaWO4 doped with Nd3+/Yb3+ phosphor emitted orange UC luminescence at 450–690 nm(2P3/2→4I15/2, 4G7/2→4I9/2,11/2,13/2) and strong near-infrared UC luminescence at 720–900 nm(4F7/2+4S3/2→4I9/2, 4F5/2+2H3/2→4I9/2, 4F3/2→4I9/2) which is the characteristic of Nd(III) ion.     

Enhanced ultraviolet upconversion in YF3：Yb^3＋/Tm^3＋ nanocrystals

Unusual intense infrared-to-ultraviolet upconversion luminescence was observed in YF3:Yb3+(20%)/Tm3+(1%) nanocrystals under 980 nm excitation. The intense ultraviolet emissions (1I6→3H6, 1I6→3F4, and 1D2→3H6) were affirmed arising from the excitation processes of five-photon and four-photon. In comparison with the bulk sample with the same chemical compositions, ultraviolet upconversion lumi-nescence of the nanocrystals was markedly enhanced. Spectral analysis indicated that the enhancement was attributed to the decrease of Judd-Ofelt parameter Ω2, which precluded the transition rate from 3F2 to 3F4, enhanced the energy transfer process and populated the 1D2 level: 3F2→3H6 (Tm3+): 3H4→1D2 (Tm3+).     

Er~(3+)-Yb~(3+)-Na~+:ZnWO_4 phosphors for enhanced visible upconversion and temperature sensing applications

The crystal structure and surface morphology of the Er³⁺/Yb³⁺/Na+:ZnWO₄ phosphors synthesized by solid state reaction method were analyzed by X-ray diffraction(XRD) and field emission scanning electron microscopy(FESEM) analysis.The frequency upconversion(UC) emission study in the developed phosphors was investigated by using 980 nm laser diode excitation.The effect of codoping in the Er³⁺:ZnWO₄ phosphors on the UC emission intensity was studied.The UC emission bands that are exhibited in the blue(490 nm),green(530,552 nm),red(668 nm) and NIR(800 nm) region correspond to the ⁴F_7/2→⁴I_15/2.²H_11/2,⁴S_3/2→⁴I_15/2,⁴F_9/2→⁴I_15/2 and ⁴I9/2→⁴I_15/2 transitions,respectively.The temperature sensing performance of the Er³⁺-Yb³⁺-Na+:ZnWO₄ phosphors was investigated based on the 2 H_11/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2 thermally coupled transitions of the Er³⁺ions.The photometric study was also carried out for the developed phosphors.     

Synthesis of NaYF4:20% Yb3+,2% Er3+,2% Ce3+@NaYF4 nanorods and their size dependent uptake efficiency under flow condition

Lanthanide doped fluorescent nanoparticles have gained considerable attention in biomedical applications. However, the low uptake efficiency of nanoparticles by cells has limited their applications. In this work, we demonstrate how the uptake efficiency is affected by the size of nanoparticles under flow conditions. Using the same size NaYF₄:20% Yb³⁺,2% Er³⁺,2% Ce³⁺ (the contents of rare earths elements are in molar fraction) nanoparticles as core, NaYF₄:20% Yb³⁺,2% Er³⁺,2% Ce³⁺@NaYF₄ core–shell structured nanorods (NRs) with different sizes of 60–224 nm were synthesized by thermal decomposition and hot injection method. Under excitation at 980 nm, a strong upconversion green emission (541 nm, ²H_11/2 → ⁴I_15/2 of Er³⁺) is observed for all samples. The emission intensity for each size nanorod was calibrated and is found to depend on the width of NRs. Under flow conditions, the nanorods with 96 nm show a maximum uptake efficiency by endothelial cells. This work demonstrates the importance of optimizing the size for improving the uptake efficiency of lanthanide-doped nanoparticles.     

Upconversion luminescence of Y2O3：Er^3＋ ,Yb^3＋ nanoparticles prepared by a homogeneous precipitation method

Y2O3： Er^3＋, Yb^3＋ nanoparticles were synthesized by a homogeneous precipitation method without and with different concentrations of EDTA 2Na. Upconversion luminescence spectra of the samples were studied under 980 nm laser excitation. The results of XRD showed that the obtained Y2O3：Er^3＋,Yb^3＋ nanoparticles were of a cubic structure. The average crystallite sizes calculated were in the range of 28-40 nm. Green and red upconversion emission were observed, and attributed to ^2H11/2,^4S3/2→^4I15/2 and ^4F9/2→^4I15/2 transitions of the ion, respectively. The ratio of the intensity of green emission to that of red emission drastically changed with a change in the EDTA 2Na concentration. In the sample synthesized without EDTA, the relative intensity of the green emission was weaker than that of the red emission. The relative intensities of green emission increased with the increased amount of EDTA 2Na used. The possible upconversion luminescence mechanisms were discussed.     

Energy transfer process of Nd3+/Ho3+ co-doped fluoride halide glasses with anion substituted multi-wavelength tunable mid-infrared luminescence

Ho³⁺ doped ZBLAN glass with 2.0 and 2.9 μm emission was prepared. In order to further improve the luminescence of Ho³⁺, halogen ions (Cl, Br, I) were introduced to reduce the maximum phonon energy and phonon state density of the sample. At the same time, Nd³⁺ was introduced to transfer the energy to Ho³⁺ pumped with a 793 nm laser (Nd³⁺:⁴F_5/2,⁴F_3/2→Ho³⁺:⁵I₆). The effect of different halogen ion on the luminescent properties of the fluoride halide glass was compared. The results show that the luminescent intensity of infrared increases with the introduction of different halogen ions. By comparison, it is found that the sample with I^– has the strongest luminescence of 1064 nm, 2.0 μm and 2.9 μm. This is consistent with the calculated J-O intensity parameters. In addition, the 2.0 and 2.9 μm emission of Ho³⁺ pumped with a 450 nm laser will not disappear. A mid-infrared sample with multi-wavelength excitation and multi-wavelength emission can be obtained. Nd³⁺/Ho³⁺ co-doped fluoride halide glasses with 1064 nm, 2.0 μm and 2.9 μm luminescence were prepared by melt quenching method. The luminescent mechanism and the energy transfer process between the two ions of Nd³⁺/Ho³⁺ co-doped fluoride halide glass were studied. The J-O parameters, luminescence lifetime and absorption emission cross-sectional area of Ho³⁺ and Nd³⁺ were calculated, respectively. It is found that the value of Ω₂ in the glass matrix increases with the introduction of different halogen ions, while Ω₄ and Ω₆ do not change obviously in different glass compositions. This is because the environment of the crystal field around the rare earth ions changes. The crystal phase and phonon energy of the sample were analyzed by X-ray diffraction pattern and a Fourier transform infrared spectrometer, respectively. Based on the above spectra and data (phonon energy is 634.71 cm⁻¹), it can be predicted that Nd³⁺/Ho³⁺ co-doped fluoride halide glass is a potential mid-infrared luminescent material.     

Energy transfer and 2 μm emission in Tm~(3+)/Ho~(3+) co-doped(Y_(0.87)La_(0.1)Zr_(0.03))_2O_3 nanopowders

(Y_(0.87)La_(0.1)Zr_(0.03))_2O_3 nanopowders doped with various concentrations of Tm~(3+) and Ho~(3+) were prepared by the citrate method. The standard cubic Y_2O_3 phase can be matched in the Tm~(3+)/Ho~(3+) co-doped(Y_(0.87)La_(0.1)Zr_(0.03))_2 O_3 nanopowders. The nanopowders exhibit average particle sizes of 40,60, 80 and 100 nm after calcinated at 900,1000,1100 and 1200℃,respectively. The energy transfer from Tm~(3+) to Ho~(3+) and the optimum fluorescence emission around 2 μm were investigated. Results indicate that the emission bands at around 1.86 and 1.95 μm correspond to ~3 F_4→~3 H_6 transition of Tm~(3+) and ~5 I_7→~5 I_8 transition of Ho~(3+), respectively.Better spectral properties were achieved in Tm~(3+)/Ho~(3+) co-doped(Y_(0.87)La_(0.1)Zr_(0.03))_2O_3 nanopowders with the average size of 100 nm obtained at the conditions of the treatment of precursors calcinated at 1200 ℃ for 2 h doped with 1.5 mol% Tm~(3+) and 1 mol% Ho~(3+).     

Effects of Bi3+ on down-/up-conversion luminescence,temperature sensing and optical transition properties of Bi3+/Er3+ co-doped YNbO4 phosphors

A series of YNbO₄:Bi³⁺ and YNbO₄:Bi³⁺/Er³⁺ phosphors were prepared by a conventional high temperature solid–state reaction method. The results of XRD and Rietveld refinement confirm that monoclinic phase YNbO₄ samples are achieved. The down-/up-conversion luminescence of Er³⁺ ions was investigated under the excitation of ultraviolet light (327 nm) and near infrared light (980 nm). Under 327 nm excitation, broad visible emission band from Bi³⁺ ions and characteristic green emission peaks from Er³⁺ ions are simultaneously observed, while only strong green emissions from Er³⁺ ions are detected upon excitation of 980 nm. Remarkable emission enhancement is observed in down-/up-conversion luminescence processes by introducing Bi³⁺ ions into Er³⁺-doped YNbO₄ phosphors. Pumped current versus up-conversion emission intensity study shows that two-photon processes are responsible for both the green and the red up-conversion emissions of Er³⁺ ion. Through the study of the temperature sensing property of Er³⁺ ion, it is affirmed that the temperature sensitivity is sensitive to the doping concentration of Bi³⁺ ions. By comparing the experimental values of the radiative transition rate ratio of the two green emission levels of Er³⁺ ions and the theoretical values calculated by Judd-Ofelt (J-O) theory, it is concluded that the temperature sensing property of Er³⁺ ions is greatly affected by the energy level splitting.     

Effect of BaF2 addition on luminescence properties of Er3+/Yb3+ co-doped phosphate glasses

Er~(3+)/Yb~(3+) co-doped phosphate glasses(P_2O_5-Al_2O_3-BaO-BaF_2-K_2O-Er_2O_3-Yb_2O_3) with varying BaF_2 content,were prepared by a conventional melt quenching technique and their spectroscopic properties were examined through the Raman, absorption, emission and decay measurements. Raman spectra(350-1400 cm~(-1)) of the Er~(3+)/Yb~(3+) co-doped phosphate glasses with varying BaF_2 content, were recorded upon laser excitation at 785 nm. Near infrared luminescence spectra were measured in the1400-1600 nm region under 970 nm diode laser excitation and characteristic band was observed at1533 nm corresponding to ~4Ⅰ_(13/2)→~4Ⅰ_(15/2) transition of Er~(3+) ion. The decay curves for the ~4Ⅰ_(13/2) level of Er~(3+)ion, were measured and the lifetime is found to decrease from 7.94 to 7.70 ms when BaF_2 content increases from 0 to 8 mol% and then increases up to 7.83 ms with further increase in BaF_2 content(12 mol%). The emission cross-section.lifetime and figure of merit for the ~4Ⅰ_(13/2)→~4Ⅰ_(15/2) transition of Er~(3+) ion were evaluated and compared to the other host matrices. The upconversion luminescence was measured and intense red emission was observed for all the studied samples.     

Saturation effect of up-conversion luminescence from erbium-doped,silicatitania sol-gel powders

The intensity of the visible up-conversion luminescence could be limited by a saturation effect produced by increased pump power. Visible up-conversion luminescence was obtained in erbium doped,silica-titania sol gel powders under dynamical pumping at 1532 nm. The saturation effect was studied for erbium radiative transitions 2H9/2→4I15/2 (410 nm),2H11/2→4I15/2 (530 nm),4S3/2→4I15/2 (550 nm),2H9/2→4I13/2 (567 nm) and 4F9/2→4I15/2 (675 nm). The recorded up-conversion luminescence decreased when increasing ex...