Effect of Yb3+ concentration on photoluminescence properties of cubic Gd2O3 phosphor

Yb³⁺ doped phosphor of Gd₂O₃ (Gd₂O₃:Yb³⁺) have been prepared by solid state reaction method. The structure and the particle size have been determined by X-ray powder diffraction measurements. The average particle size of the phosphor is in between 35 and 50 nm. The particle size and structure of the phosphor was further confirmed by TEM analysis. The visible and NIR luminescence spectra were recorded under the 980 nm laser excitation. The visible upconversion luminescence of Yb³⁺ ion was due to cooperative luminescence and the presence of rare earth impurity ions. The cooperative upconversion and NIR luminescence spectra as a function of Yb³⁺ ion concentration were measured and the emission intensity variation with Yb³⁺ ion concentration was discussed. Yb³⁺ energy migration quenched the cooperative luminescence of Gd₂O₃:Yb³⁺ phosphor with doping level over 5%, while the NIR emission luminescence continuously increases with increasing Yb³⁺ ion concentration.     

Fabrication and luminescence behavior of phosphate glass ceramics co-doped with Er3+ and Yb3+

Transparent phosphate glass ceramics co-doped with Er³⁺ and Yb³⁺ in the system P₂O₅Li₂OCaF₂TiO₂ were successfully synthesized by melt-quenching and subsequent heating. Formation of the nanocrystals was confirmed by X-ray powder diffraction. Judd–Ofelt analyses of Er³⁺ ions in the precursor glasses and glass ceramics were performed to evaluate the intensity parameters Ω_2,4,6. Under 975 nm excitation, intense upconversion (UC) and infrared emission (1545 nm) were observed in the glass ceramics by efficient energy transfer from Yb³⁺ to Er³⁺. The luminescence processes were explained and the emission cross section was calculated by Fuchtbauer–Ladenburg (F–L) formula. The results confirm the potential applications of Er³⁺/Yb³⁺ co-doped glass ceramics as laser and fiber amplifier media.     

Upconversion luminescence in Tm3+/Yb3+co-doped lead tungstate tellurite glasses

This work reports the upconversion luminescence properties of Tm³⁺/Yb³⁺ ions in lead tungstate tellurite (LTT) glasses. Judd–Oflet intensity parameters have been obtained from the absorption band intensities of Tm³⁺ singly-doped and Tm³⁺/Yb³⁺ co-doped LTT glasses. The spontaneous emission probabilities, radiative lifetimes and branching ratios for ¹G₄ and ³H₄ emission levels of Tm³⁺ have been determined. Upconversion luminescence has been observed by exciting the samples at 980 nm (Yb³⁺:²F_7/2→²F_5/2) at room temperature. Four upconversion emission bands corresponding to the ¹G₄→³H₆ (477 nm), ¹G₄→³F₄ (651 nm), ¹G₄→³H₅ (702 nm) and ³H₄→³H₆ (810 nm) transitions have been identified. The relative variation in the intensities of upconversion bands, the different channels responsible for upconversion spectra and the effect of Yb³⁺ ions concentration on the upconversion luminescence of Tm³⁺ ions have also been discussed.     

Upconversion photoluminescence properties of SrY2(MoO4)4:Er3+/Yb3+ phosphors synthesized by a cyclic microwave-modified sol–gel method

SrY_2−x(MoO₄)₄:Er³⁺/Yb³ phosphors with doping concentrations of Er³⁺ and Yb³⁺ (x = Er³⁺ + Yb³⁺, Er³⁺ = 0.05, 0.1, 0.2 and Yb³⁺ = 0.2, 0.45) have been successfully synthesized by a cyclic microwave-modified sol–gel method, and the upconversion photoluminescence properties have been investigated. Well-crystallized particles showed a fine and homogeneous morphology with particle sizes of 1–3 μm. Under excitation at 980 nm, SrY₂(MoO₄)₄:Er³⁺/Yb³⁺ particles exhibited a strong 525-nm, weak 550-nm emission bands in the green region, and a very weak 655-nm emission band in the red region. The possible mechanism of the green and red emissions was discussed in detail under consideration of a two-photon process. The Raman spectra of the particles indicated the presence of strong peaks at both higher and lower frequencies.     

Temporal dynamics of upconversion luminescence in Er3+, Yb3+ co-doped crystalline KY(WO4)2 thin films

Crystalline Er³⁺ and Yb³⁺ singly and doubly doped KY(WO₄)₂ thin films were grown by low-temperature liquid-phase epitaxy. Absorption, luminescence, excitation and temporal evolution measurements were carried out for both Er³⁺ and Yb³⁺ transitions from 10 K to room temperature. Green Er³⁺ upconversion luminescence was observed after Yb³⁺ and Er³⁺ excitation. The mechanisms responsible for the upconversion phenomena detected in each case were identified.     

Hydrothermal synthesis and the enhanced blue upconversion luminescence of NaYF4:Nd3+,Tm3+,Yb3+

Nd³⁺, Tm³⁺ and Yb³⁺ co-doped NaYF₄ upconversion (UC) material was synthesized by the hydrothermal method. The structure of the sample was characterized by the X-ray diffraction, and its UC luminescence properties were investigated in detail. Under the 980 nm semiconductor laser excitation, its UC spectra exhibited distinct emission peaks at 451 nm, 475 nm and 646 nm respectively. On the basis of the comparison of UC spectra between NaYF₄:Nd³⁺,Tm³⁺,Yb³⁺ and NaYF₄:Tm³⁺,Yb³⁺, it was indicated that the existence of Nd³⁺ ion enhanced the blue emission intensity. The law of luminescence intensity versus pump power proved that the blue emission at 475 nm, and the red emission at 646 nm were the two-photon processes, while the blue emission at 451 nm was a three-photon process.     

Optical temperature sensor through infrared excited blue upconversion emission in Tm3 +/Yb3 + codoped Y2O3

An analysis of the intense blue upconversion emission at 476 and 488 nm in Tm^3 +/Yb^3 + codoped Y₂O₃ under excitation power density of 86.7 W/cm² available from a diode laser emitting at 976 nm, has been undertaken. Fluorescence intensity ratio (FIR) variation of temperature-sensitive blue upconversion emission at 476 and 488 nm in this material was recorded in the temperature range from 303 to 753 K. The maximum sensitivity derived from the FIR technique of the blue upconversion emission is approximately 0.0035 K^? 1. The results imply that Tm^3 +/Yb^3 + codoped Y₂O₃ is a potential candidate for the optical temperature sensor.     

Infrared to visible upconversion luminescence in Er3+/Yb3+ doped titanate glass prepared by containerless processing

Er³⁺ doped TiO₂–La₂O₃ glasses modified by ZrO₂ have been successfully fabricated by the containerless method with incorporated Yb³⁺ ions as sensitizers. Under the excitation of 980 and 808 nm diode lasers, visible emissions centered at 534, 554 and 674 nm are observed, which are assigned to the Er³⁺ transitions of ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2, respectively. The emission signals are so strong that they can be observed by naked eyes even at pumping power as low as 20 mW. Measurements of pump-power dependent intensity and time-resolved decay behavior of upconversion luminescence show that two-photon excited state absorption (ESA) and energy transfer (ET) between rare earth ions are the predominant mechanisms for upconversion emissions. Besides, the intensity of upconversion luminescence has been enhanced by increasing the concentration of ZrO₂ in these rare earth doped bulk titanate glasses.     

Increase of the blue upconversion emission in YAG:Tm3+ nanopowders by codoping with Yb3+ ions

The YAG nanopowders were prepared by a co-precipitation method using nitrate and ammonium hydrogen carbonate as raw materials. To obtain homogenous precipitate, reverse-strike (adding salt solutions to the precipitant solution) technique was adopted. Therefore, single (Tm³⁺) and codoped (Tm³⁺–Yb³⁺) YAG nanopowders with a size between 40–90 nm have been obtained.Blue upconversion emission at around 480 nm has been found in YAG: Tm³⁺ nanopowders under excitation to the ³H₄ level of Tm³⁺ at around 800 nm. However, this upconversion emission in nanopowders codoped with Tm³⁺–Yb³⁺ ions is increased by a factor of about 10. The analysis of the temporal evolution of the involved levels and the dependence of the upconversion intensity on the pump power at 800 nm allowed to distinguish the upconversion mechanism. In YAG: Tm³⁺ nanopowders the upconversion mechanism is due to excited state absorption processes. However, in the codoped samples, Yb³⁺ ions acts as the sensitizers; in consequence, the blue upconversion is strongly increased.     

Microwave sol–gel derived NaCaGd(MoO4)3:Er3+/Yb3+ phosphors and their upconversion photoluminescence properties

Ternary molybdate NaCaGd_1−x(MoO₄)₃:Er³⁺/Yb³⁺ phosphors with the proper doping concentrations of Er³⁺ and Yb³⁺ (x = Er³⁺ + Yb³⁺, Er³⁺ = 0, 0.05, 0.1, 0.2 and Yb³⁺ = 0, 0.2, 0.45) were successfully synthesized by microwave sol–gel method for the first time. Well-crystallized particles formed after heat-treatment at 900 °C for 16 h showed a fine and homogeneous morphology with particle sizes of 3–5 μm. The optical properties were examined comparatively using photoluminescence emission and Raman spectroscopy. Under excitation at 980 nm, the doped particles exhibited a strong 525-nm emission band, a weak 550-nm emission band in the green region, which correspond to the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions, and a very weak 655-nm emission band in the red region, which corresponds to the ⁴F_9/2 → ⁴I_15/2 transition. The optimal Yb³⁺:Er³⁺ ratio was obtained to be 9:1, as indicated by the composition-dependent quenching effect of Er³⁺ ions. The pump power dependence of upconversion emission intensity and Commission Internationale de L’Eclairage chromaticity coordinates of the phosphors were evaluated in detail.     

Optical characterization of Er3+and Yb3+ co-doped barium fluorotellurite glass

Spectroscopic studies of Er³⁺/Yb³⁺ co-doped (Ba,La)-fluorotellurite glass composition have been carried out using standard experimental and theoretical methods. Quantitative analyses of the room temperature absorption and emission spectra as well as the emission lifetimes yield various important spectroscopic parameters such as the radiative decay rates, fluorescence branching ratios, and emission/absorption cross sections. In addition, internal radiative quantum yields have been determined for the infrared emission at 1571 nm and for the upconversion emission at 547 nm. The influence of various non-radiative properties such as multiphonon relaxation, concentration quenching, and quenching by hydroxyl radicals have also been quantitatively estimated and correlated with the observed spectral properties. The comparative studies with the other composition of tellurite and different glasses showed that present glass composition could be a potential candidate for the broadband amplifier.     

Quasi-one dimensional Er3+–Yb3+ codoped single-crystal MoO3 ribbons: Synthesis,characterization and up-conversion luminescence

The quasi-one dimensional (Q1D) Er³⁺–Yb³⁺ codoped single-crystal MoO₃ ribbons with width range from 1 to 5 μm, and maximum length about 30 μm have been synthesized by the vapor transport method. The samples were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscope, and luminescence spectra. By a 975 nm laser diode (LD) as excitation source, the blue, green and red emission bands centered at about 408, 532, 553 and 657 nm were detected, which attributed to the ²H_9/2 → ⁴I_15/2, ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺, respectively. The three-, and two-photon process was responsible for the blue, green and red up-conversion emissions mechanism for the Q1D Er³⁺–Yb³⁺ codoped single-crystal MoO₃ ribbons, respectively. The results suggested that the Q1D Er³⁺–Yb³⁺ codoped single-crystal MoO₃ ribbons will have potential applications in remote bio-imaging and surface enhanced Raman scattering.     

Comparative Investigation on Nanocrystal Structure and Luminescence Properties of Gadolinium Molybdates Codoped with Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>

This paper reports on the comparative investigation of nanocrystal structure and luminescence properties of Er³⁺/Yb³⁺-codoped gadolinium molybdate nanocrystals Gd₂(MoO₄)₃ and Gd₂MoO₆ synthesized by the Pechini method with citric acid and ethylene glycol. Their crystallization, structure transformation, and morphologies have been investigated by X-ray diffraction, thermogravimetric/differential scanning calorimetry, and transmission electron microscopy. It is noticed that Er³⁺/Yb³⁺-codoped monoclinic Gd₂(MoO₄)₃ nanocrystals have shown an intense upconversion through a sintering of the organic complex precursor at 600°C. Furthermore, it transforms to orthorhombic Gd₂(MoO₄)₃ when the precursor is sintered at 900°C. In counterpart of monoclinic Gd₂MoO₆, however, the monoclinic structure remains unchanged when the precursor is sintered at a temperature ranging from 600°C to 900°C. Intense visible emissions of Er³⁺ attributed to the transitions of ²H_11/2, ⁴S_3/2–⁴I_15/2 at 520 and 550 nm, and ⁴F_9/2–⁴I_15/2 at 650 nm have been observed upon an excitation with a UV source and a 980 nm laser diode, and the involved mechanisms have been explained. It is quite interesting to observe obvious differences both in the excitation and the upconversion emission spectra of Er³⁺/Yb³⁺-codoped Gd₂(MoO₄)₃ respectively with monoclinic and orthorhombic structure. The quadratic dependence of fluorescence on excitation laser power has confirmed that two-photons contribute to upconversion of the green–red emissions.     

Synthesis and luminescence properties of Er3+-doped Lu3Ga5O12 nanocrystals

The concentration-dependent luminescence properties of sol–gel-derived nanocrystalline Lu_3(1?x)Er_3xGa₅O₁₂ powders (where x=0.01, 0.05 and 0.1) have been studied. Laser-excited luminescence spectra, emission decays and upconversion luminescence of Er³⁺-doped Lu₃Ga₅O₁₂ nanocrystalline samples have been measured. The decay curve of the (²H_11/2,⁴S_3/2) emission exhibits a non-exponential behavior presumably due to cross-relaxation process. Moreover, near-infrared to visible upconversion luminescence has been observed in the green region for 1.0 mol% Er³⁺ ions in Lu₃Ga₅O₁₂ nanocrystals upon 815 nm excitation. The power dependence of the anti-Stokes luminescence suggests that upconversion is probably achieved through the sequential absorption of two photons. To the best of our knowledge, this is the first report on the preparation and optical properties of Er³⁺-doped Lu₃Ga₅O₁₂ in the form of nanocrystalline powders.     

Up conversion luminescence of Yb3+–Er3+ codoped CeO2 nanocrystals with imaging applications

The effects of Yb³⁺ doping on up conversion in Yb³⁺–Er³⁺ co-doped cerium oxide nanocrystals are reported. Green emission around 545 and 560 nm attributed to the ²H_11/2, ⁴S_3/2→⁴I_15/2 transitions and red emission around 660 and 680 nm due to ⁴F_9/2→ ⁴I_15/2 transitions under 975 nm excitation were studied at room temperature. Both green and red emission intensities increase as the Yb³⁺ concentration increases from 0%. Emission strength starts to decrease after the Yb³⁺ concentration exceeds a critical amount. The green emission strength peaks around 1% Yb³⁺ concentration while the red emission strength peaks around 4%. An explanation of competition between different decay mechanisms is presented to account for the luminescence dependence on Yb³⁺ concentration. Also, the application of up converting nanoparticles in biomedical imaging is demonstrated.     

Blue upconversion luminescence in 12 CaO·7 Al2O3:Tm3 +/Yb3 + polycrystals

The effect of Yb^3 + concentration on the fluorescence of 12 CaO·7 Al₂O₃:Tm^3 +/Yb^3 + polycrystals is investigated. Under the excitation of 980 nm laser, the strong blue (477 nm) emission band is observed and attributed to ¹G₄ → ³H₆ of Tm^3 +. The ratio of blue to red emission increases with the increasing of Yb^3 + and remains constant at 10 mol% Yb^3 +. The pump dependence and upconversion mechanisms show that the two-photon cooperative upconversion process is responsible for the enhancement of the blue upconversion emission. The Commission Internationale de l'eclairage chromaticity coordinates (x, y) illustrate that the 12 CaO·7 Al₂O₃:1 mol% Tm^3 +/10 mol% Yb^3 + can emit high-purity blue light.     

Erbium doping into silicate glasses to form luminescent optical layers for photonics applications

Here we summarise results of our research on the Er-containing thin surface layers in the silicate glasses and on the effect of the layers’ composition on their luminescence properties (emission at 1535 nm) in the wavelength region widely used in photonics. The optical layers were fabricated by Er³⁺ (melt)⇔Li⁺/Na⁺ (glass substrate) ion exchange in the specially designed Li₂O containing silicate glasses using various conditions (including annealing of the samples) to obtain a set of layers with diverse distribution of the Er³⁺ ions. Changes in the chemical composition of the prepared layers were suggested to avoid the concentration quenching effect and to improve their luminescence properties; special attention was paid to presence of hydrogen in the layers that may decrease the emission intensity. Rutherford Backscattering Spectroscopy and Elastic Recoil Detection were used to obtain detailed information on migration of erbium and hydrogen through the glass matrix, respectively. Photoluminescence spectra of the fabricated samples were measured (excitation at 980 nm) to examine the desired emission around 1535 nm.     

Upconversion emission enhancement in Er/Yb-codoped BaTiO3 nanocrystals by tridoping with Li ions

Er³⁺/Yb³⁺/Li⁺-tridoped BaTiO₃ nanocrystals were prepared by a sol-gel method to improve the upconversion (UC) luminescence of rare-earth doped BaTiO₃ nanoparticles. Effects of Li⁺ ion on the UC emission properties of the Er³⁺/Yb³⁺/Li⁺-tridoped BaTiO₃ nanocrystals were investigated. The results indicated that tridoping with Li⁺ ion enhanced the visible green and red UC emissions of Er³⁺/Yb³⁺-codoped BaTiO₃ nanocrystals under the excitation of a 976 nm laser diode. X-ray diffraction and decay time of the UC luminescence were studied to explain the reasons of the enhancement of UC emission intensity. X-ray diffraction results gave evidence that tridoping with Li⁺ ion decreased the local symmetry of crystal field around Er³⁺, which increased the intra-4f transitions of Er³⁺ ion. Moreover, lifetimes in the intermediate ⁴ S_3/2 and ⁴I_11/2 (Er) states were enhanced by Li⁺ ion incorporation in the lattice. Therefore, it can be concluded that Li⁺ ion in rare-earth doped nanocrystals is effective in enhancing the UC emission intensity.     

Luminescence properties of Eu3+ and Sm3+ coactivated Gd(III) tungstate phosphor for light-emitting diodes

Rare-earth ions coactivated red phosphors Gd_0.2RE_1.8(WO₄)₃ (RE=Eu³⁺ and Sm³⁺) were synthesized by conventional solid-state reaction using boric acid as a flux agent. The samples were characterized by X-ray diffractometer (XRD), energy-dispersive X-ray spectrometer (EDS) and luminescence spectrometer (LS). The results showed that the Eu–Sm system exhibits higher emission intensity than those of the Eu single-doped system and Sm separate-doped system under ultraviolet (UV) radiation. Samarium(III) ions are effective in broadening and strengthened absorptions around 400 nm. Furthermore, it exhibits enhanced luminescence emission. when the mole ratio of boric acid is about 0.16, the luminescence capability is optimum. Two strongest lines at ultraviolet (394 nm) and blue (465 nm) in excitation spectra of these phosphors match well with the output wavelengths of UV and blue GaN-based light-emitting diodes (LEDs) chips.     

Blue upconversion luminescence of CaMoO4:Li+/Yb3+/Tm3+ phosphors prepared by complex citrate method

Li⁺/Tm³⁺/Yb³⁺ co-doped CaMoO₄ upconversion (UC) phosphor was prepared by complex citrate-gel method and UC luminescence properties were investigated. Li⁺/Tm³⁺/Yb³⁺ co-doped CaMoO₄ has intense blue emission induced by ¹G₄??³H₆ transition at 476?nm that is improved 10 times more than that of Li⁺ undoped sample and weak red emission at 647 nm generated by ³F₂??³H₆ transition under excitation at 980?nm. The optimum doping concentration of Li⁺ ions was investigated and UC mechanism of Li⁺/Tm³⁺/Yb³⁺ co-doped CaMoO₄ was discussed in detail.