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.     

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.     

Synthesis of CaWO4：Eu3＋ phosphor powders via ethylene glycol route and its optical properties

Eu3+ doped CaWO4 with tetragonal system were prepared at comparatively low temperature (125 ?C) in ethylene glycol medium. The phosphor was further investigated by X-ray diffractometer (XRD), photoluminescence spectrophotometer (PL), Fourier transform infra red (FT-IR) spectroscopy and transmission electron microscopy (TEM). XRD analysis indicated a decrease in the unit cell volume of CaWO4 with increasing Eu3+ ion concentration. It indicated the homogeneous substitution of Ca2+ ions in CaWO4 by the Eu3+ ions. TEM images showed that the particle size ranged from 20 to 200 nm and it could extend the application of the nanoparticles. The photoluminescence study showed that the intensity of electric dipole transition (5D0→7F2) at 614 nm dominated over the magnetic dipole transition (5D0→7F1) at 592 nm. The optimum concentration of Eu3+ for the highest luminescence was found to be 20 at.%. The as prepared samples were found to be dis-persible in water and methanol.     

Upconversion luminescence of KGd（MoO_4）_2：Er~（3＋）,Yb~（3＋） powder prepared by Pechini method

Er3+ doped potassium gadolinium molybdate (KGM) phosphor with sensitizer Yb3+ ion was synthesized by the Pechini method using citric acid and ethylene glycol. The crystallization processes of the phosphor precursors were characterized by X-ray diffraction (XRD) and thermogravimetry-differential scanning calorimetry (TG-DSC), which indicated that ultrafine uniform crystallites of KGM:Er,Yb were obtained by sintering the precursors at above 650 ℃ for 5 h. Upconversion luminescence (UL) spectra of the samples ...     

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+).     

Up-conversion processes of rare earth ions in heavy metal glasses

Heavy metal lead germanate glasses doubly doped with Yb3+ and Ln3+ ions(Ln=Er,Tm) were investigated.Up-conversion spectra of Er3+ and Tm3+ were registered under diode-laser excitation of Yb3+.Up-conversion luminescence bands corresponded to 4S3/2→4I15/2(green) and 4F9/2→4I15/2(red) transitions of Er3+ as well as 1G4→3H6(blue) and 3H4→3H6(NIR) transitions of Tm3+,respectively.     

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.     

Upconversion luminescence of Yb3+/Ho3+/Er3+/Tm3+ co-doped KGd(WO4)2 powders

Different lanthanide ions (Yb3+/Ho3+/Er3+/Tm3+) codoped KGd(WO4)2 phosphors were prepared by high-temperature solid-state reaction. The upconversion luminescence properties of two-ion and three-ion co-doped KGd(WO4)2 phosphors were investigated in detail. The concentration quenching effect of the two-ion co-doped KGd(WO4)2 phosphors was studied, and the optimum concentration of Ho3+, Er3+ and Tm3+ are 2 mol.%, 2 mol.% and 3 mol.%, respectively. The Yb3+/Ho3+/Tm3+ co-doped KGd(WO4)2 sample is the best white ...     

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.     

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.     

Emission enhancement and color modulation of Tm(Ho)/Yb codoped Gd_2(MoO_4)_3 thin films via the use of multilayered structure

The multilayered structure thin films(Gd_2(MoO_4)_3:Ho(Tm)/Yb@Gd_2(MoO_4)_3:Yb)) were prepared through sol-gel and spin-coating method,while the average thinness was nearly 140 nm.We investigated the up-conversion luminescence of Gd2(MoO_4)3:Ho(Tm)/Yb@Gd2(MoO_4)3:Yb thin films,The results show that the double-layer structured thin films are able to increase the emission intensity.The fluorescence enhancement factors of the luminescence from Gd2(MoO_4)3:Ho/Yb@Gd2(MoO_4)3:Yb thin films,located at540 and 662 nm,reach 7.5 and 4.3,respectively.And the enhancement factors of emissions located at450,475 and 650 nm(Gd_2(MoO_4)3:Tm/Yb@Gd_2(MoO_4)_3:Yb)) reach 9,2 and 2,respectively.The considerable enhancement is due to the suppression of surface quenching and energy harvesting via the Yb ions in the outer shell.In addition,the emission color of thin films can be modulated from yellow to blue via tuning the number of Gd2(MoO_4)3:Ho/Yb and Gd2(MoO_4)3:Tm/Yb layers,which provides a feasible strategy to tune the up-conversion emission color.     

Quenching mechanism of Er~(3+) emissions in Er~(3+)-and Er~(3+)/Yb~(3+)-doped SrAl_(12)O_(19) nanophosphors

Nanoscaled SrAl12O19:Er3+ and SrAl12O19:Yb3+,Er3+ phosphors were synthesized by a combustion method.The emission intensities of every sample were compared by a new method with the emission of codoped Gd3+ ions as a reference.Compared with their bulk material prepared by the solid-state reaction method,a higher Er3+ quenching concentration,as high as 20%,was observed in the nanoscaled phosphors for both visible(VIS) and near infrared(NIR) emissions.The higher quenching concentration in both VIS and NIR regio...     

Up-conversion luminescence of Tm3+/Yb3+ co-doped oxy-fluoride glasses

The oxy-fluorosilicate glasses co-doped with Yb3+/Tm3+ were prepared.The absorption spectra were recorded.The Tm3+ ion showed two absorption bands,with one at 774 nm due to 1G4→3H6 transition and the other at 667 nm due to 1G4→3F4 transition.The energy transfer between Tm3+ ion and Yb3+ ion and the up-conversion fluorescence of Tm3+ ion were investigated using 980 nm LD excitation.The results showed that the blue and red emissions were three-photon absorption processes corresponding with 1G4→3H6 and 1G4→3F4...     

Novel phosphors of Eu~(3+), Tb~(3+) or Tm~(3+) activated LaBGeO_5

Rare earth borogermanates as a group of stable compounds provided various potential properties important for modern sciences. Among the properties of interests, luminescence was manifested due to the variability of rare earth elements and the compounds constituted an important group of potential candidate. In this work, novel phosphors of Eu3+, Tb3+ or Tm3+ doped LaBGeO5 with the stillwellite type structure were synthesized by the solid state reaction method. Their X-ray and UV excitation luminescent proper...     

Phase-, shape- and size-controlled synthesis of NaYF4：Yb3＋,Er3＋ nanoparticles using rare-earth acetate precursors

Hexagonal-phase NaYF4：Yb3＋,Er3＋ upconversion nanoparticles（UCNPs） with a uniform size distribution were synthesized using rare-earth acetates as precursors. The effects of reaction temperature and time on the phase transition process of the UCNPs were systematically studied. Based on the evolution of particle morphology and phase with temperature and time, it could be concluded that the transition from cubic phase to hexagonal phase for NaYF4：Yb3＋,Er3＋ UCNPs was consistent with a dissolution/recrystallization process. In addition, the shape and size of the UCNPs could be controlled by adjusting the solvent ratio and the precursor ratio, respectively.     

Upconversion Luminescence Properties of Ho^3＋, Tm^3＋, Yb^3＋ Co-Doped Nanocrystal NaYF4 Synthesized by Hydrothermal Method

Nanocrystal of upconversion （UC） phosphor Ho^3＋, Tm^3＋ , and Yb^3＋ co-doped NaYF4 was prepared by the hydrothermal method in the presence of the complexing agent EDTA. Under 980 nm diode laser excitation, the impact of different concentrations of Ho^3＋ ion on the UC luminescence intensity was discussed. The law of luminescence intensity versus pump power shows that the 474 nm blue emission, 538 nm green emission, and 642 nm red emission are all due to the two-photon process, while the 450 nm blue emission is a three-photon process. The UC mechanism and processes were also analyzed. The sample was characterized by transmission electron microscopy （TEM） and X-ray diffraction （XRD）. The result shows that Ho^3＋ ,Tm^3＋ , and Yb^3＋ co-doped NaYF4 prepared by the hydrothermal method exhibits a hexagonal nanocrystal.     

Ultraviolet to near-infrared energy transfer in NaYF_4:Nd~(3+),Yb~(3+) crystals

To convert ultraviolet(UV) light into near-infrared(NIR) light in phosphors is demanded for the development of solar cells.A series of NaYF_4:Nd~(3+),Yb~(3+) white powder samples were prepared via the hydrothermal method.The crystal structure and photoluminescence properties of the samples were carefully studied using X-ray diffractometry(XRD) and photoluminescence spectra.The excitation and emission spectra of NaYF_4:Nd~(3+),Yb~(3+) samples and the luminescence decay curves of Nd~(3+) and Yb~(3+) revealed an efficient energy transfer process from Nd~(3+) to Yb~(3+).This process resulted in the Yb~(3+) NIR fluorescent emission at 980 nm.Moreover,the lifetime of the Nd~(3+4)F_(3/2) level decreased with the increase of Yb~(3+) doping concentration.The build-up time of the decay curves of the Yb~(3+2)F_(5/2) level further verified the energy transfer process.Meanwhile,energy transfer efficiency based on different Yb~(3+) doping concentrations was achieved.