Role of Yb and Tm ions in upconversion emission of Tb under 798 and 980 nm laser excitations in Tb-Tm-Yb doped tellurite glass

Upconversion emission and energy transfer processes in singly, doubly and triply doped tellurite glasses have been studied under 798 and 980 nm laser excitations. Emissions have been observed at 482, 544, 584, 655 nm and at 477, 655, 698, 800 nm corresponding to Tb³⁺: ⁵D₄ → ⁷F₆, ⁷F₅, ⁷F₄, ⁷F_J (J = 0, 1, 2, 3) and Tm³⁺: ¹G₄ → ³H₆, ¹G₄ → ³F₄, ³F₃ → ³H₆, ³H₄ → ³H₆ transitions, respectively. Among Tm³⁺, Yb³⁺and Tb³⁺ ions only Tm³⁺ has a ground state absorption at 798 nm excitation due to ³H₄ ← ³H₆ transition. For 980 nm excitation only Yb³⁺ can absorb the incident radiation. However, for both types of excitations, emission from all the three ions Tb, Yb and Tm has been observed. Possible mechanisms are proposed as follows: under 798 nm excitation Tm³⁺ ions are excited which excite Yb³⁺ ions through energy transfer. Finally “cooperative energy transfer” from a pair of Yb³⁺ ions to Tm³⁺ and Tb³⁺ ions takes place. Under 980 nm excitation Yb³⁺ ions absorb the incident energy and excite Tm³⁺ and Tb³⁺ ions via cooperative energy transfer. Variation of emission intensity with the ion concentrations of Yb³⁺, Tm³⁺ and Tb³⁺ has been studied. The lifetime of the ¹G₄ level has also been measured.     

The up-conversion properties of Yb and Er doped Y4Al2O9 phosphors

Er³⁺ doped and Yb³⁺/Er³⁺ co-doped Y₄Al₂O₉ phosphors are prepared by the sol-gel method. The effect of dopant concentration on the structure and up-conversion properties is investigated by X-ray diffraction (XRD) and photoluminescence, respectively. XRD pattern indicates that the sample structure belongs to monoclinic. Under 980 nm excitation, the green and red up-conversion emissions are observed and the emission intensities depended on the Yb³⁺ ion concentration. The green up-conversion emissions decrease with the increase of Yb³⁺ concentration, while red emission increases as Yb³⁺ concentration increases from 0 to 8 at% and then decreases at high Yb³⁺ concentration. The mechanisms of the up-conversion emissions are discussed and results shows that in Er³⁺ and Yb³⁺/Er³⁺ co-doped system, cross-relaxation (CR) and energy transfer (ET) processes play an important role for the green and red up-conversion emissions.     

Influence of Yb doping concentration on upconversion luminescence of Er in Lu2O3 phosphor

Cubic phase Lu₂O₃:Er³⁺/Yb³⁺ nanocrystal phosphors were prepared by sol–gel method. Fourier transform infrared (FT-IR) spectra were measured to evaluate the vibrational feature of the samples. Green and red radiations were observed upon 980 nm diode laser excitation. Laser power and Er³⁺ or Yb³⁺ doping concentration dependence of upconversion luminescence were studied to understand upconversion mechanisms. Excited state absorption, cross relaxation and energy transfer processes are the possible mechanisms for the visible emissions.     

Optical spectroscopy of Yb/Er codoped NaY(WO4)2 crystal

Erbium and ytterbium codoped double tungstates NaY(WO₄)₂ crystals were prepared by using Czochralski (CZ) pulling method. The absorption spectra in the region 290-2000 nm have been recorded at room temperature. The Judd-Ofelt theory was applied to the measured values of absorption line strengths to evaluate the spontaneous emission probabilities and stimulated emission cross sections of Er³⁺ ions in NaY(WO₄)₂ crystals. Intensive green and red lights were measured when the sample were pumped by a 974 nm laser diode (LD), especially, the intensities of green upconversion luminescence are very strong. The mechanism of energy transfer from Yb³⁺ to Er³⁺ ions was analyzed. Energy transfer and nonradiative relaxation played an important role in the upconversion process. Photoexcited luminescence experiments are also fulfilled to help analyzing the transit processes of the energy levels.     

Luminescence spectroscopy of Er-doped and Er, Yb-codoped LaPO4 single crystals

LaPO₄ single crystals lightly doped with Er³⁺, and codoped with Er³⁺ and Yb³⁺ have been grown by spontaneous nucleation in a lead phosphate flux. Absorption and luminescence spectra have been measured in the visible and near-IR regions and the excited state dynamics has been studied upon pulsed laser excitation. The obtained results have allowed the evaluation of the effective emission cross-sections around 1.5 μm, that have been found to be similar to important oxide laser crystals doped with Er³⁺. Efficient visible upconversion has been observed upon excitation at 980 nm in the codoped crystals. This behaviour is attributed to Yb³⁺-Er³⁺ energy transfer processes.     

Up-conversion white light of Tm/Er/Yb tri-doped CaF2 phosphors

Tm³⁺/Er³⁺/Yb³⁺ tri-doped CaF₂ phosphors were synthesized using a hydrothermal method. The phosphors were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and up-conversion (UC) emission spectra. After annealing, the phosphors emitted white light under a 980 nm continuous wave diode laser (CW LD 2 W) excitation. As the excitation power density changed in the range of 20-260 W/cm², the chromaticity coordinates of the UC light of the phosphor Ca_0.885Tm_0.005Er_0.01Yb_0.1F₂ fell well in the white region of the 1931 CIE diagram. For the proportion of red, green and blue (RGB) in white light is strict, key factors for achieving UC white light, such as host materials, rare earth ions doping concentrations, annealing temperatures, as well as the excitation power densities, were investigated and discussed.     

Visible upconversion emission and non-radiative direct Yb to Er energy transfer processes in nanocrystalline ZrO2:Yb,Er

Wide band gap Yb³⁺ and Er³⁺ codoped ZrO₂ nanocrystals have been synthesized by a modified sol-gel method. Under 967 nm excitation strong green and red upconversion emission is observed for several Er³⁺ to Yb³⁺ ions concentration ratios. A simple microscopic rate equation model is used to study the effects of non-radiative direct Yb³⁺ to Er³⁺ energy transfer processes on the visible and near infrared fluorescence decay trends of both Er³⁺ and Yb³⁺ ions. The microscopic rate equation model takes into account the crystalline phase as well as the size of nanocrystals. Nanocrystals phase and size were estimated from XRD patterns. The rate equation model succeeds to fit simultaneously all visible and near infrared fluorescence decay profiles. The dipole-dipole interaction parameters that drive the non-radiative energy transfer processes depend on doping concentration due to crystallite phase changes. In addition the non-radiative relaxation rate (⁴I_11/2→⁴I_13/2) is found to be greater than that estimated by the Judd-Ofelt parameters due to the action of surface impurities. Results suggest that non-radiative direct Yb³⁺ to Er³⁺ energy transfer processes in ZrO₂:Yb,Er are extremely efficient.     

Transfer and backtransfer processes in Yb-Er codoped Strontium Barium Niobate glass-ceramics

The forward and backward energy transfer processes in Strontium Barium Niobate glass-ceramics double doped with Yb³⁺ and Er³⁺ ions have been studied. In these samples the rare earth ions are incorporated into the nanocrystals with an average size of 50 nm. Using laser excitation at 950 nm is possible to excite selectively the Yb³⁺ ions and detect emission due to these ions (at 1040 nm) or combined with the Er³⁺ ions (at 980 nm). In previous works, the energy transfer processes between these ions in different matrices have been analyzed in order to improve the emission at 1550 nm, but these analyses are restricted to fast migration processes among ions. In this fast migration regimen the results are valid only for larger concentrations. However, in this work the dynamics of these transfer processes has been carried out using a general method called “transfer function model”. The parameters which characterize these processes have been obtained and it has been possible to explain the important increase of the emission at 1550 nm due to the co-doping with Yb³⁺ ions. This analysis is valid for any range of doping concentrations.     

Influence of carbon templates and Yb concentration on red and green luminescence of uniform Y2O3:Yb/Er hollow microspheres

Uniform Yb³⁺ and Er³⁺-codoped Y₂O₃ hollow microspheres were synthesized via urea co-precipitation using carbon spheres as templates. Intense red emission (⁴F_9/2→⁴I_15/2) and weak green emission (²H_11/2, ⁴S_3/2→⁴I_15/2) of Er³⁺ were observed for the Yb³⁺ and Er³⁺-codoped Y₂O₃ hollow microspheres under 980 nm infrared excitation. The integrated intensity of visible emission and the ratio of red to green were found to be strongly dependent on the amount of carbon sphere templates and the concentration of Yb³⁺ ions. The amount of carbon sphere templates also plays an important role in adjusting the size of crystallite. Multi-phonon relaxation resulted from the absorbents (OH⁻ and CO₃²⁻) on the surface of the crystallite, and efficient occur of energy transfer processes and cross-relaxation between Er³⁺ and Yb³⁺ are responsible for the enhancement of intensity ratio of red to green emission. Interestingly, for higher concentration of Yb³⁺ ions, the green emission is assigned to a three-phonon process in Y₂O₃:Yb/Er hollow microspheres, which also could result in the increase of the red to green emission ratio. An explanation to account for these behaviors was presented.     

Up-conversion luminescence of Er/Yb/Nd-codoped tellurite glasses

Up-conversion luminescence and energy transfer (ET) processes in Nd³⁺-Yb³⁺-Er³⁺ triply doped TeO₂-ZnO-Na₂O glasses have been studied under 800 nm excitation. Intense green up-conversion emissions around 549 nm, which can be attributed to the Er³⁺: ⁴S_3/2→⁴I_15/2 transition, are observed in triply doped samples. In contrast, the green emissions are hardly observed in Er³⁺ singly doped and Er³⁺-Yb³⁺ codoped samples under the same condition. Up-conversion luminescence intensity exhibits dependence of Yb₂O₃-concentration and Nd₂O₃-concentration. Up-conversion mechanism in the triply doped glasses under 800 nm pump is discussed by analyzing the ET among Nd³⁺, Yb³⁺ and Er³⁺. And a possible up-conversion mechanism based on sequential ET from Nd³⁺ to Er³⁺ through Yb³⁺ is proposed for green and red up-conversion emission processes.     

Energy transfer and frequency upconversion in Yb3+–Er3+-doped PbO-GeO2 glass containing silver nanoparticles

We report the infrared-to-visible frequency upconversion in Er³⁺–Yb³⁺-codoped PbO-GeO₂ glass containing silver nanoparticles (NPs). The optical excitation is made with a laser at 980 nm in resonance with the ²F_5/2→²F_7/2 transition of Yb³⁺ ions. Intense emission bands centered at 525, 550, and 662 nm were observed corresponding to Er³⁺ transitions. The simultaneous influence of the Yb³⁺→Er³⁺ energy transfer and the contribution of the intensified local field effect due to the silver NPs give origin to the enhancement of the whole frequency upconversion spectra.     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

Synergistic upconversion effect in NaYF4:Yb,Tm nanorods under dual excitation of 980 nm and 808 nm

NaYF₄:Yb³⁺,Tm³⁺ nanorods are prepared with hydrothermal method. The upconversion luminescent properties are investigated under dual excitation of 980 nm and 808 nm. The blue emission is observed at about 475 nm under dual excitation. The intensity is 2.6 times higher than the total intensity of the two corresponding single wavelength excitations, showing a synergistic upconversion effect occurring there. The dual wavelength excitation not only effectively decreases non-radiative relaxation pumped by 980 nm but also reduces the rate of the back energy transfer from Tm³⁺ to Yb³⁺ pumped by 808 nm. The result provides a possible new way to further improve the upconversion efficiency of rare earth doped phosphor.     

Hydrothermal synthesis of BaYF5:Yb/Er upconversion luminescence submicrospheres by a surfactant-free aqueous solution route

BaYF₅:Yb³⁺/Er³⁺ upconversion (UC) luminescence submicrospheres have been synthesized by the hydrothermal synthesis method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), scanning probe microscope (SPM), transmission electron microscope (TEM), laser diffraction particle analyzer (LDPA) and UC emission spectra. The as-prepared highly crystalline BaYF₅:Yb³⁺/Er³⁺ submicrospheres are of uniform size depending on different reaction temperatures and reaction times. It is found that the usage of fluoride source NaBF₄ plays the crucial key in the formation of submicrosphere. Under the 980 nm excitation, the UC emission transitions for ⁴F_9/2→⁴I_15/2 (red), ²H_11/2, ⁴S_3/2→⁴I_15/2 (green) in the BaYF₅:Yb³⁺/Er³⁺ submicrospheres came from two-, two-, and two-photon UC processes, respectively. Further, the effects of Yb³⁺ ion concentration, size and surface of as-prepared submicrospheres, and pumping power on the UC luminescence properties of BaYF₅:Yb³⁺/Er³⁺ have also been discussed.     

Upconversion luminescence of colloidal solution of Y2O3 nano-particles doped with trivalent rare-earth ions

We have studied upconversion luminescence of colloidal solution of Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺. Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺ show sintering and agglomeration, because they are synthesized by firing a hydroxy carbonate precursor. Colloidal solution of Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺ is prepared through two-step dispersion process and the average diameter of the primary nano-particles is about 50 nm. Under excitation with 980-nm laser diode, upconversion luminescence of colloidal solution of the primary Y₂O₃ nano-particles codoped with 1 mol% Er³⁺ and 5 mol% Yb³⁺ in methyl isobuthyl ketone strongly appeared near 660 nm and weakly near 550 nm.     

Energy transfer and infrared-to-visible upconversion luminescence of Er/Yb-codoped halide modified tellurite glasses

We report on the energy transfer and frequency upconversion spectroscopic properties of Er³⁺-doped and Er³⁺/Yb³⁺-codoped TeO₂-ZnO-Na₂O-PbCl₂ halide modified tellurite glasses upon excitation with 808 and 978 nm laser diode. Three intense emissions centered at around 529, 546 and 657 nm, alongwith a very weak blue emission at 410 nm have clearly been observed for the Er³⁺/Yb³⁺-codoped halide modified tellurite glasses upon excitation at 978 nm and the involved mechanisms are explained. The quadratic dependence of fluorescence on excitation laser power confirms the fact that the two-photon contribute to the infrared to green-red upconversion emissions. And the blue upconversion at 410 nm involved a sequential three-photon absorption process.     

Optical and EPR study of BaY2F8 single crystals doped with Yb

Optical and electron paramagnetic resonance study have been carried out on BaY₂F₈ single crystals doped with Yb ions at 0.5 and 10 mol%. The crystals have been obtained using the Czochralski method modified for fluoride crystal growth. Optical transmission measurements in the range of 190-3200 nm and photoluminescence measurements were carried out at room temperature. Absorption spectra of BaY₂F₈ single crystals doped with Yb due to the ²F_7/2→²F_5/2 transitions have been observed in the 930-980 nm range. To analyze the possible presence of Yb²⁺ ions in the investigated crystals, irradiation with γ-quanta with a dose of 10⁵ Gy have been performed. The observed photoluminescence bands show usual emission in IR and other one in VIS, being an effect of cooperative emission of Yb³⁺ ions and energy up-conversion transitions of photons from IR to UV-vis(visible) due to hoping process between energy levels of paired Yb³⁺ and Er³⁺, where Er³⁺ ions are unintentional dopants. The EPR spectra of BaY₂F₈:Yb 10 mol% consist of many overlapping lines. They have been analyzed in terms of spin monomers, pairs, and clusters. The angular dependence of the resonance lines positions have been studied also to find the location of coupled ytterbium ions in the crystal structure.     

Optical thermometry through green and red upconversion emissions in Er/Yb/Li:ZrO2 nanocrystals

Variations of fluorescence intensity ratio of green (generated from Er^{3+ 2}H_11/2 and ⁴S_3/2 levels) and red (generated from the sublevels of Er^{3+ 4}F_9/2 level) upconversion emissions in Er³⁺/Yb³⁺/Li⁺:ZrO₂ nanocrystals have been studied as a function of temperature under 976 nm laser diode excitation. In the temperature range of 323-673 K, the maximum sensitivities of about 0.0134 K^− 1 and 0.0104 K^− 1 are obtained by using green and red emission, respectively. Er³⁺/Yb³⁺/Li⁺:ZrO₂ nanocrystals show potential application value in nanoscale thermal sensor.     

The effect of Y co-doping on the persistent up-conversion luminescence of the ZrO2:Yb,Er nanomaterials

The effect of the defects due to the charge compensation obtained with the yttrium co-doping to the ZrO₂:Yb³⁺,Er³⁺ up-converting phosphors was studied. The materials were prepared with the combustion method. The materials purity was analyzed with the FT-IR spectroscopy. The crystal structure was studied with the X-ray powder diffraction and the crystallite sizes were estimated with the Scherrer formula. Up-conversion luminescence was excited at room temperature with an IR-laser at 970 nm. The up-conversion luminescence spectra showed red (650-685 nm) and green emission (520-560 nm) due to the ⁴F_9/2→⁴I_15/2 and (²H_11/2,⁴S_3/2)→⁴I_15/2 transitions of Er³⁺, respectively. Persistent up-conversion luminescence was observed both in the Yb³⁺,Er³⁺ and Y³⁺,Yb³⁺,Er³⁺ doped materials.     

Spectral properties and energy transfer of Yb,Er:GdVO4 crystal

GdVO₄ single crystal co-doped with Yb³⁺ and Er³⁺ was grown by the Czochralski method. The X-ray powder diffraction pattern of Yb,Er:GdVO₄ crystal confirms that the as-grown crystal is isostructural with pure GdVO₄ crystal. Its polarized absorption spectra and non-polarized fluorescence spectra were measured at room temperature. The absorption band at 984 nm for π-polarization has an FWHM of about 36 nm, which is favorable for InGaAs LD laser pumping. The spectrum properties of Er³⁺ in Yb,Er:GdVO₄ crystal were investigated based on Judd–Ofelt theory. There is strong energy transfer from Yb³⁺ to Er³⁺ in this crystal. When excited with 980 nm radiation, this crystal emitted strong fluorescence at about 1529 nm and 552.5 nm. The total energy transfer rate and efficiency from Yb³⁺ to Er³⁺ is 3.33 ms^-1 and 67%, respectively. The energy transfer between Er³⁺ and Yb³⁺ ions is a multistep transfer process, and was investigated based on a random-walk model. The investigation result shows that there is strong cooperative-sensitization effect from Yb³⁺ to Er³⁺, which is the main upconversion energy-transfer process in this crystal. PACS 42.70.Hj; 81.10.Fq; 42.55.Rz