Visualization of 2-μm radiation by BiF<Subscript>3</Subscript>:Ho<Superscript>3+</Superscript> and BiF<Subscript>3</Subscript>:Ho<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> ceramics

A series of ceramic samples of the compositions BiF₃:1%Ho³⁺, BiF₃:4%Ho³⁺, BiF₃:1%Ho³⁺ + 1%Yb³⁺, and BiF₃:1%Ho³⁺ + 3%Yb³⁺ is synthesized and the conversion of Tm:YLF laser radiation (λ = 1908 nm) is studied. The luminescence spectra exhibit bands in the regions of 490, 545, and 650 nm. The kinetic measurements of the afterglow of the green and red bands show that the population of the ⁵S₂ and ⁵F₄ states in the BiF₃:1%Ho³⁺ samples occurs due to successive absorption of excitation photons, while the ⁵F₅ level of Ho³⁺ is populated due to the ion–ion interaction. Codoping with Yb³⁺ leads to a decrease in the visualization threshold power density to 2 W/cm².     

Visible upconversion and infrared luminescence investigations of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powders doped with Er<Superscript>3+</Superscript>, Yb<Superscript>3+</Superscript> and Zn<Superscript>2+</Superscript> ions

Alumina (Al₂O₃) powders doped with Er³⁺, Yb³⁺ and Zn²⁺ ions have been prepared by a low-temperature combustion synthesis technique. The phase purity and crystalline structure of the combustion products are confirmed by powder X-ray diffraction. An efficient frequency upconversion in the visible region and the emission in the infrared (IR) region respectively corresponding to the ²H_11/2, ⁴S_3/2→⁴I_15/2, ⁴F_9/2→⁴I_15/2 and ⁴I_13/2→⁴I_15/2 transitions upon direct excitation with a CW laser lasing at ∼980 nm are discussed. The enhancement observed in the intensity of the upconversion emission bands in the visible region and the emission band in the IR region due to the presence of Yb³⁺ and Zn²⁺ in Er³⁺:Al₂O₃ powders is reported and explained in detail.     

Photoluminescence of sol–gel-derived Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> thin-film phosphors with Mg<Superscript>2+</Superscript> and Al<Superscript>3+</Superscript> co-doping

Red-light-emitting Y₂O₃:Eu³⁺ thin-film phosphors were synthesized using a sol–gel process. The effect of Mg²⁺ and Al³⁺ co-dopants on the Y₂O₃:Eu³⁺ thin-film phosphor photoluminescence (PL) property was investigated. At a certain concentration, both Mg²⁺ and Al³⁺ co-dopants were found to further enhance the PL emission intensity of Y₂O₃:Eu³⁺ thin-film phosphors. The optimum PL emission intensity was observed in Y₂O₃:12%Eu³⁺, 7%Mg²⁺ and Y₂O₃:12%Eu³⁺, 2%Al³⁺ phosphor films. From our results, the enhancement of the emission intensity by the Mg²⁺ and Al³⁺ co-dopants is explained in terms of the creation of defect states near the Y(4d+5s) conduction band, which overlap with the Eu³⁺ charge-transfer state (CTS). The overlapping leads to CTS broadening and consequently induces higher absorption and hence an increase of the emission intensity. From X-ray diffraction results, we have found that there is no additional phase formed in the co-doped phosphor films. PACS 68.55.Ln; 78.55.-m; 81.20.Fw     

Frequency upconversion properties of Ag: TeO<Subscript>2</Subscript>–ZnO nanocomposites codoped with Yb<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

Yb³⁺–Tm³⁺ codoped tellurite glasses containing silver nanoparticles (NPs) were synthesized and characterized using transmission electron microscopy and optical techniques. The samples’ composition and the nucleation of NPs were investigated using electron diffraction and energy dispersive spectroscopy. For the optical experiments, the samples were excited using a diode laser operating at 980 nm, in resonance with the Yb³⁺ transition ²F_7/2→²F_5/2. Photoluminescence (PL) bands corresponding to Tm³⁺ transitions were observed at 480, 650, and 800 nm due to the Yb³⁺→ Tm³⁺ energy transfer. PL enhancement was achieved by heat-treatment of the samples at 325°C during different time intervals. The growth of the PL bands correlates with the increase of the silver NPs concentration. The relevant mechanisms contributing for the PL characteristics are discussed.     

Anti-Stokes Luminescence in LiYF<Subscript>4</Subscript>:Ho<Superscript>3+</Superscript>, Yb<Superscript>3+</Superscript> Ceramics Excited at 1.93 μm

Conversion of IR radiation of a Tm:YAP laser with a wavelength of 1930 nm into visible light by ceramics of composition LiY_(1–x–y) Ho _x Yb _y , where х = 1–5 mol % and y = 0–15 mol %, is demonstrated. It is shown that the threshold power density of IR light visualization decreases with increasing concentration of Ho³⁺ ions, while additional doping of ceramic samples with Yb³⁺ ions changes the anti-Stokes luminescence spectrum. The threshold power density of visualization of the Tm:YAP laser radiation decreases with increasing concentration of holmium ions and is I_thr ≈ 0.8 W cm^–2 in the samples of composition LiYF₄:5%Ho³⁺–15%Yb³⁺.     

Spectroscopic Properties of LiNbO<Subscript>3</Subscript>:Tm<Superscript>3+</Superscript> Crystal in the 1650–1970 nm Wavelength Range

Taking into account the Stark structure of optical spectrum of the impurity ion, the theoretical study of spectroscopic properties of LiNbO₃:Tm³⁺ crystal in the wavelength range of 1650–1970 nm was carried out. The wave functions of the Stark sublevels of both ground ³H₆ and the first excited ³F₄ manifolds of the Tm³⁺ ion were constructed in the LSJM-representation, the line strengths induced by indirect electric-dipole transitions were calculated, and the main spectroscopic characteristics of emission and absorption spectra of impurity ion were determined.     

Photorefractive properties of optical waveguides in Fe:LiNbO<Subscript>3</Subscript> crystals produced by O<Superscript>3+</Superscript> ion implantation

The photorefractive properties of optical planar waveguides in Fe:LiNbO₃ crystals fabricated by O³⁺ ion implantation are investigated. Two-wave mixing experiments are carried out for both the waveguide and the bulk. The results show that the measured gain coefficients are almost identical for the waveguiding layer and the substrate. In the waveguide, the response time could be reduced by one order of magnitude, with respect to the bulk, at the same power level of the incident light.     

Enhancing up conversion luminescence effect of β-NaYF<Subscript>4</Subscript>: Yb<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> by Li<Superscript>+</Superscript> ion doped approach

Up-conversion (UC) is a photoluminescence process which converts few low energy photons to a higher energy photon. This process has more potential usages in many different fields like bioimaging, solar spectrum tuning, and security encoding. Nowadays, researches about UC mostly focusing on biomedical signory and synthesis of nanoparticles. The synthesis of NaYF₄ nanoparticles executed under series of pH value condition results in different morphology and photoluminescence effect. Samples in low pH value created better consequent and quality than the specimen which had higher pH value. In addition, we observed NaYF₄ samples of doping Li⁺, realizing that the action of distorting in the local symmetry around rare-earth ions is caused by Li⁺ doping. The NaYF₄ microparticles which doped higher concentration of Li⁺ has strong fluorescence properties and intensities compared with their corresponding group of Li⁺-free, the blue emission 479 nm luminescence intensities and 454 nm luminescence intensities in NaYF₄:Yb³⁺, Tm³⁺ microparticles doped 20 mol% Li⁺ are enhanced 3 and 8 times, separately. And violet emission luminescence intensities around 345 and 360 nm are about 10 and 7 times, respectively. The result indicated that the improved UC luminescence of NaYF₄:Yb³⁺. Tm³⁺ microparticles with Li⁺ doping have potentially applications.     

Mechanism of the Yb<Superscript>2+</Superscript> → Yb<Superscript>3+</Superscript> valence transition in ytterbium nanofilms upon chemisorption of CO and O<Subscript>2</Subscript> molecules on their surface

The dependences of the work function of ytterbium nanofilms with a thickness ranging from 1 to 32 monolayers on the amount of CO or O₂ molecules chemisorbed on their surface have been investigated experimentally. It has been found that these dependences have a pronounced nonmonotonic character. The mechanism of the Yb²⁺ → Yb³⁺ valence transition, which occurs upon the chemisorption of CO or O₂ molecules on the surface of ytterbium nanofilms, has been developed using the results of this study together with the previously obtained data.     

Pr<Superscript>3+</Superscript>-doped Tl<Subscript>3</Subscript>PbBr<Subscript>5</Subscript>: a non-hygroscopic,non-linear and low-energy phonon single crystal for the mid-infrared laser application

This letter presents the optical and spectroscopic properties of a new low-energy phonon, moisture-resistant and non-linear Pr³⁺:Tl₃PbBr₅ single crystal. Though only weakly doped with Pr³⁺ ions, centimetre-size and good-quality single crystals could be grown and analyzed. Absorption and emission spectra as well as fluorescence kinetics were registered in the mid-infrared spectral domain. Strong luminescence at around 4–5.5 μm was observed and assigned to the ³H₅→³H₄ transition of the Pr³⁺ ions. The high value of the resulting emission cross section associated with the long lifetime of the ³H₅ emitting level indicates that this material could be a good candidate for the development of a broadly tunable mid-infrared solid-state laser source.     

Porous sulfated metal oxide SO<Subscript>4</Subscript><Superscript>2−</Superscript>/Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> as an anode material for Li-ion batteries with enhanced electrochemical performance

Sulfated metal oxide SO₄ ^2?/Fe₂O₃ was prepared by a novel facile sol–gel method combined with a subsequent heating treatment process. The as-synthesized products were analyzed by XRD, FTIR, and FE-SEM. Compared with the unsulfated Fe₂O₃, the agglomeration of particles has been alleviated after the incorporation of SO₄ ^2?. Interestingly, the primary particle size of the SO₄ ^2?/Fe₂O₃ (about 5 nm) is similar to its normal counterparts even after the calcination treatment. More importantly, SO₄ ^2?/Fe₂O₃ exhibits a porous architecture, which is an intriguing feature for electrode materials. When used as anode materials in Li-ion batteries, SO₄ ^2?/Fe₂O₃ delivered a higher reversible discharge capacity (992 mAh g^?1), with smaller charge transfer resistance, excellent rate performance, and better cycling stability than normal Fe₂O₃. We believed that the presence of SO₄ ^2? and porous architecture should be responsible for the enhanced electrochemical performance, which could provide more continuous and accessible conductive paths for Li⁺ and electrons.     

Visible up-conversion and NIR luminescence studies of LiAl<Subscript>5</Subscript>O<Subscript>8</Subscript>:Er phosphor co-doped with Yb<Superscript>3+</Superscript> and Zn<Superscript>2+</Superscript>

The frequency up-conversion, an efficient laser emission and amplification in Er³⁺:LiAl₅O₈ phosphors co-doped with Yb³⁺ and Zn²⁺ phosphor powders in the 520–560, 640–680 nm regions and at ∼1.5 μm, respectively, have been reported. The emission corresponds to the ²H_11/2, ⁴S_3/2→⁴I_15/2, ⁴F_9/2→⁴I_15/2 and ⁴I_13/2→⁴I_15/2 transitions upon direct excitation into the intermediated ⁴I_11/2 level using ∼980 nm radiation from a CW laser. Possible mechanisms involved for the up-conversion processes based on the energy level matching scheme, the pump-power dependence and the dynamical behaviour have been discussed. The effect of the addition of Yb³⁺ and Zn²⁺ for the amplification in the 1.5 μm eye-safe telecommunication window has been elaborated and characterized in detail.     

Cooperative downconversion and near-infrared luminescence of Tb<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript> codoped lanthanum borogermanate glasses

In the present paper, we investigate the near-infrared (NIR) luminescence of Tb³⁺–Yb³⁺ codoped lanthanum borogermanate (LBG) glasses under visible and ultraviolet light excitation. The results indicate that NIR quantum cutting occurs through cooperative energy transfer from Tb³⁺ to Yb³⁺ ions when only 4f ⁸ levels of Tb³⁺ ions are excited in the wavelength region of 300–490 nm. The highest quantum efficiency under the excitation ⁵ D ₄ level of Tb³⁺ at 484 nm is 146%. Ultraviolet excitation that populates the charge transfer band (CTB) of Yb³⁺ near 270 nm does not result in quantum cutting as the fast nonradiative decay from CTB to ² F _5/2 level dominates. These materials are expected to be used as a converting layer for silicon solar cells to enhance their efficiency by splitting each high-energy photon into two NIR photons.     

Enhanced photoluminescence from Cr<Superscript>3+</Superscript> centers in α-sapphire coated with LiNbO<Subscript>3</Subscript>(:Fe) and LiTaO<Subscript>3</Subscript> films

A LiNbO₃(:Fe) or LiTaO₃ film is sandwiched between a (012)-oriented -sapphire wafer and an amorphous Al₂O₃ or SiO₂ film using pulsed laser deposition. After annealing at 1000 °C in O₂, the film becomes a c-oriented single-domain ferroelectric. This sandwich structure shows an enhanced photoluminescence from trace amounts of Cr³⁺ centers in the host -sapphire (R-line emission at 691 nm). Spectral analyses suggest that both strong space-charge and photorefractive effects of the LiNbO₃(:Fe) or LiTaO₃ film cause a change in the crystal field of the host -sapphire, which increases the transition probability of Cr³⁺ and thus leads to an enhancement of the R-line intensity. The result has prospective applications in laser and optical integrated devices. PACS 77.55.+f; 78.20.-e; 78.55.-m     

Optical Flow-Through Sensor for the Determination of Norfloxacin Based on Emission of KMnO<Subscript>4</Subscript>–Na<Subscript>2</Subscript>SO<Subscript>3</Subscript>–Tb<Superscript>3+</Superscript> System

A simple and selective method to determine norfloxacin using an optical flow-through sensor has been developed. The present sensor was prepared by packing anionic ion exchange resin in a glass tube, followed by introducing KMnO₄ solution to the glass tube for immobilization on resin. The optical sensor is based on the emission intensity from the Tb(III) solution sensitized by norfloxacin. The excitation of norfloxacin occurred by the chemiluminescence from the reaction of KMnO₄ and Na₂SO₄ solutions. The effects of pH, concentration of Tb(III) ion, KMnO₄ and Na₂SO₄ solutions and flow rate of the norfloxacin solution on the chemiluminescence intensity were studied to find the optimum experimental conditions. The emission intensity increased linearly with increasing norfloxacin concentration from 1.0 × 10⁻³ to 1.0 × 10⁻⁸ M and the detection limit (3σ) was 8.7 × 10⁻⁹. The applicability of the present method was demonstrated by determination of norfloxacin in various pharmaceutical preparations and serum sample.     

Spectroscopic analysis of Pr<Superscript>3+</Superscript> crystal-field transitions in YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Yttrium aluminium borate single crystals, doped with 1 and 4 mol% of Pr³⁺, were analyzed in the wave number range 500–25000 cm⁻¹ and temperature range 9–300 K by means of high-resolution Fourier transform spectroscopy. In spite of the complex spectra, exhibiting broad and split lines, the energy level scheme was obtained for several excited manifolds. The careful analysis of the spectra as a function of the temperature allowed us to identify most of the sublevels of the ground manifold. The thermally induced line shift, well described by a single-phonon coupling model, could be exploited to provide information about the energy of the phonons involved. The orientation of the dielectric ellipsoid and of the dipole moments associated to a few transitions was also determined from linear dichroism measurements. The experimental data were fitted in the framework of the crystal-field theory, but the agreement was not satisfactory, as already reported for Pr³⁺ ion in other matrices. Additional discrepancies came from the dichroic spectra analysis and the line splitting, possibly associated to hyperfine interaction. Some causes which might be responsible for the difficulties encountered in the Pr³⁺ ion theoretical modelling are discussed.     

Hyperfine Interactions in Pb<Superscript>3+</Superscript>F<Stack><Subscript>8</Subscript><Superscript>−</Superscript></Stack>F<Stack><Subscript>a</Subscript><Superscript>−</Superscript></Stack> clusters in fluorite crystals

The parameters of hyperfine interactions in Pb³⁺F ₈ ^? F _a ^? tetragonal clusters of MeF₂ crystals (Me=Ca, Sr, Ba) are interpreted. The contributions of the spin polarization to the parameters of the proper hyperfine interaction and additional (ligand) hyperfine interactions are calculated in the approximation of weak binding between a charge-compensating ion F _a ^? and a cubic fragment in the tetragonal cluster. It is demonstrated that correct inclusion of the contributions from the spin polarization to the ligand isotropic hyperfine interaction for the F _a ^? ion leads to anomalously large parameters of this interaction for MeF₂ crystals. These results are in agreement with experimental data.     

Hydrothermal synthesis,characterization, and luminescence of Ca<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>5</Subscript>:RE (RE = Eu<Superscript>3+</Superscript>, Tb<Superscript>3+</Superscript>, Dy<Superscript>3+</Superscript>) nanofibers

Ca₂B₂O₅:RE (RE = Eu³⁺, Tb³⁺, Dy³⁺) nanofibers were synthesized by the hydrothermal reaction method. The structural refinement was conducted on the base of the X-ray powder diffraction (XRD) measurements. The surface properties of the Ca₂B₂O₅:RE (RE = Eu³⁺, Tb³⁺, Dy³⁺) nanofibers were investigated by the measurements such as the scanning electron microscope (SEM), transmission electron microscope (TEM), and the energy dispersive spectrum (EDS). The nanofiber has a diameter of about 100 nm and a length of several micrometers. The luminescence properties such as photoluminescence excitation (PLE) and emission spectra (PL), decay lifetime, color coordinates, and the absolute internal quantum efficiency (QE) were reported. Ca₂B₂O₅:Eu³⁺ nanofibers show the red luminescence with CIE coordinates of (x = 0.41, y = 0.51) and the luminescence lifetime of 0.63 ms. The luminescence of Ca₂B₂O₅:Tb³⁺ nanofibers is green color (x = 0.29, y = 0.53) with the lifetime of 2.13 ms. However, Dy³⁺-doped Ca₂B₂O₅ nanofibers present a single-phase white-color phosphor with the fluorescence decay of 3.05 ms. Upon near-UV excitation, the absolute quantum efficiency is measured to be 65, 35, and 37 % for Eu³⁺-, Tb³⁺-, Dy³⁺-doped Ca₂B₂O₅ nanofibers, respectively. It is suggested that Ca₂B₂O₅:RE (RE = Eu³⁺, Tb³⁺, Dy³⁺) nanofibers could be an efficient phosphor for lighting and display.     

Calix[4]arene Based Dual Fluorescent Sensor for Al<Superscript>3+</Superscript> and S<Subscript>2</Subscript>O<Subscript>7</Subscript><Superscript>2−</Superscript>

Specific functionalized calix[4]arene based fluorescent chemosensor was synthesized for cations and anions binding efficiency examination. Receptor C4MA displayed strong affinity for Al³⁺and S₂O₇ ^2? with enhanced fluorescence intensity. The selective response of C4MA was investigated in the presence of different co-existing competing ions. The limit of detection (LOD) of Al³⁺and S₂O₇ ^2? was calculated as 2.8?×?10^?6 M and 2.6?×?10^?7 M respectively. Sensor C4MA forms (1:1) stoichiometric complex with both Al³⁺ and S₂O₇ ^2? and their binding constants were calculated as 12.1?×?10⁴ and 8.3?×?10³ respectively. Complexes were also characterized through FT-IR spectroscopy.

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