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.     

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.     

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     

Probing the Catalytic Center of TiO<Subscript>2</Subscript>/SO<Subscript>4</Subscript><Superscript>2−</Superscript> Solid Superacid Catalyst by X-Band In Situ High-Temperature EPR Spectroscopy

Paramagnetic centers of the solid superacid catalyst in the sulfated TiO₂ are prone to the electron paramagnetic resonance (EPR) spectroscopy. The induction of the catalytic-active sites in TiO₂ powder presubmerged in H₂SO₄ solution as a function of the calcinated temperature of 293–873 K is investigated by X-band in situ continuous-wave EPR measurements. Sulfated-acid sites composed of the Ti³⁺ ion are formed upon calcination. The overall experimental results show that the population of these sites goes uphill with the elevating temperature, reaches a maximum at ~623 K and decreases afterward to close zero. During the process, the decomposition of the TiO₂/SO₄ ²⁻ leads to the formation of Ti³⁺ species and then to the increasing EPR signal amplitude, and the consecutive decomposition of the sulfur at higher temperature (>650 K) to the diminishing signal. The X-ray diffraction indicates that the introduction of SO₄ ²⁻ stabilizes the geometric structure in the anatase phase.     

A Multi-Responsive Naphthalimide-Based “Turn-on” Fluorescent Chemosensor for Sensitive Detection of Trivalent Cations Ga<Superscript>3+</Superscript>, Al<Superscript>3+</Superscript> and Cr<Superscript>3+</Superscript>

A new multifunctional chemosensor 1, (E)-2-(((2-hydroxynaphthalen-1-yl)methylene)amino)-1H-benzo[de]isoquinoline-1,3(2H)-dione, based on naphtalimide and naphthaldehyde was developed, which showed the fluorescence responses to trivalent metal ions (Ga³⁺, Al³⁺ and Cr³⁺). Sensor 1 detected and differentiated selectively trivalent metal ions Ga³⁺, Al³⁺ and Cr³⁺ by fluorescence enhancement at different emissions. The association constant of Ga³⁺-2?1 complex is the highest one among those of the organic chemosensors reported, to date. The sensing mechanisms for Ga³⁺, Al³⁺ and Cr³⁺ were explained by UV-vis titrations, Job plots, ESI-mass analyses and theoretical calculations.     

Optimizing after-glow luminescent parameters of Sr<Subscript>4</Subscript>Al<Subscript>14</Subscript>O<Subscript>25</Subscript>:Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript>, by sol–gel method and combustion process

Strontium aluminates are viewed as a promising persistent luminescent materials. There are many researches on strontium aluminates, including SrAl₂O₄, Sr₄Al₁₄O₂₅. Between these two phases, Sr₄Al₁₄O₂₅ shows much better properties than SrAl₂O₄. The traditional way to synthesize Sr₄Al₁₄O₂₅ is the solid state reaction. However, it exists few problems, especially non-homogeneous product. As a result, there are two methods chosen to make homogeneous precursor. One is sol–gel method, the other is combustion with Urea as a fuel. Boric acid is added as a flux in both method. In this study, combustion process is found to be a better way for synthesizing Sr₄Al₁₄O₂₅. We change the temperature, synthetic method. The samples are finely grinded and used for XRD analysis, photoluminescence measurement, and after-glow decay curve to figure out the optimizing luminescent parameters.     

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.     

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     

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.     

White Light Emitting MZr<Subscript>4</Subscript>(PO<Subscript>4</Subscript>)<Subscript>6</Subscript>:Dy<Superscript>3+</Superscript> (M = Ca,Sr, Ba) Phosphors for WLEDs

A series of MZr₄(PO₄)₆:Dy³⁺ (M = Ca, Sr, Ba) phosphors were prepared by the solid state diffusion method. Confirmation of the phase formation and morphological studies were performed by X-ray powder diffraction (XRD) measurements and scanning electron microscopy, respectively. Photoluminescence (PL) properties of these phosphors were thoroughly analyzed and the characteristic emissions of Dy³⁺ ions were found to arise from them at an excitation wavelength of 351 nm. The PL emission spectra of the three phosphors were analyzed and compared. The CIE chromaticity coordinates assured that the phosphors produced cool white-light emission and hence, they are potential candidates for UV excited white-LEDs (WLEDs).

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<Superscript>57</Superscript>Fe emission Mössbauer spectroscopy following dilute implantation of <Superscript>57</Superscript>Mn into In <Subscript>2</Subscript>O<Subscript>3</Subscript>

Emission Mössbauer spectroscopy has been utilised to characterize dilute ⁵⁷Fe impurities in In ₂O₃ following implantation of ⁵⁷Mn (T _1/2 = 1.5 min.) at the ISOLDE facility at CERN. From stoichiometry considerations, one would expect Fe to adopt the valence state 3 + , substituting In ³⁺, however the spectra are dominated by spectral lines due to paramagnetic Fe²⁺. Using first principle calculations in the framework of density functional theory (DFT), the density of states of dilute Fe and the hyperfine parameters have been determined. The hybridization between the 3d-band of Fe and the 2p band of oxygen induces a spin-polarized hole on the O site close to the Fe site, which is found to be the cause of the Fe²⁺ state in In ₂O₃. Comparison of experimental data to calculated hyperfine parameters suggests that Fe predominantly enters the 8b site rather than the 24d site of the cation site in the Bixbyite structure of In ₂O₃. A gradual transition from an amorphous to a crystalline state is observed with increasing implantation/annealing temperature.     

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.     

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.     

Fluorescent Property of the Gd<Superscript>3+</Superscript>-Doped Terbium Complexes and Crystal Structure of [Tb(TPTZ)(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>]Cl<Subscript>3</Subscript>·3H<Subscript>2</Subscript>O

The complex of Tb(TPTZ)Cl₃·3H₂O was synthesized by adding the ethyl alcohol solution of TbCl₃ (1 mmol) to the solution of 2,4,6-tris-(2-pyridyl)-s-triazine(TPTZ,1 mmol) with constant stirring. The solution which had been filtered was kept at the room temperature for 4 weeks, and then a kind of transparent crystal was formed. Besides, nine kinds of solid complexes in the different molar proportion of terbium to gadolinium had been synthesized by adopting the similar method mentioned above. It was inferred from the elemental analysis and rare earth complexometry that the composition of these complexes is (Tb_xGd_y)(TPTZ)Cl₃·3H₂O (x : y = 0.9 : 0.1, 0.8 : 0.2, 0.7 : 0.3, 0.6 : 0.4, 0.5 : 0.5, 0.4 : 0.6, 0.3 : 0.7, 0.2 : 0.8, 0.1 : 0.9). The absorption spectra and photoluminescence of the complexes were determined in dimethylsulfoxide (DMF), which showed that the excitation of the complexes is mostly ligand based. The triplet state energy level of TPTZ was measured, indicating that the lowest excitation state energy level of Tb(III) and the triplet state energy level of TPTZ match well each other. The fluorescent data indicated that the fluorescent emission intensity of Tb³⁺ ions would be enhanced in the complexes after terbium was doped with Gd³⁺ ion. When x : y was 0.5 : 0.5, the fluorescent emission intensity was the largest. The result obtained by testing the X-ray diffraction of the monocrystal revealed that the molecular formula of the mono-crystal complex is [Tb(TPTZ)(H₂O)₆]Cl₃·3H₂O. The number of metal ion coordinates is nine, and the tridentate TPTZ and six water molecules are bonded with terbium respectively. Besides, it also revealed that the monocrystal belongs to the monoclinic system, and space group Cc with the following unit cell parameters is a = 1.4785 (3) nm, b = 1.0547 (2) nm, c = 1.7385 (4) nm, β = 94.42 (3)°, V = 2.7028 (9) nm³ and Z = 4.     

Upconversion in Ho<Superscript>3+</Superscript>-doped YbF<Subscript>3</Subscript> particle prepared by coprecipitation method

YbF₃ particles doped with Ho³⁺ were synthesized by coprecipitation method, from which the ultraviolet and visible emission bands of the Ho³⁺ and the 480 nm cooperative upconversion emission of Yb³⁺–Yb³⁺ are observed under 980 nm excitation. Under the same excitation power, the emission intensity of Ho³⁺ in coprecipitation method is enhanced by about two times comparing to that in solid-state reaction method. The novel ultraviolet and violet emissions of the Ho³⁺ are firstly obtained which are centered at 360 (⁵G₂→⁵I₈),391 (³K₇→⁵I₈),412 (⁵G₄→⁵I₈), and 446 nm (⁵G₅→⁵I₈). The luminescence decay profiles of 545 and 652 nm visible emissions were obtained with a 980 nm pulsed laser. The excitation power dependence of the emission intensity was also measured and intensity saturation was observed. Based on the level structures of Ho³⁺, two- and three-photon processes are suggested to perform populations of ⁵S₂ and ⁵G₃ (Ho³⁺) levels, respectively. The dominant upconversion mechanism may be attributed to a cooperative sensitization process of two excited states of Yb³⁺ and energy transfers from Yb³⁺ to Ho³⁺.     

110 W ceramic Nd<Superscript>3+</Superscript> : Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> laser

A high-power, continuous-wave 0.6% Nd³⁺-doped ceramic Y₃Al₅O₁₂ (Nd:YAG) laser has been developed. 110 W laser output at 1064 nm was obtained, with a slope efficiency of about 41%. The M² factor was found to be around 6. The laser performance of the ceramic laser material was found to compare favorably with that obtained with single crystal Nd:YAG. PACS 42.55.-f; 42.55.Xi; 42.70.Hj     

Mössbauer studies of spatial spin-modulated structure and hyperfine interactions in multiferroic Bi<Superscript>57</Superscript>Fe<Subscript>0.10</Subscript>Fe<Subscript>0.85</Subscript>Cr<Subscript>0.05</Subscript>O<Subscript>3</Subscript>

Results of Mössbauer investigations on ⁵⁷Fe nuclei in multiferroic material Bi⁵⁷Fe_0.10Fe_0.85Cr_0.05O₃ in the temperature range from 5.2 to 300 K are presented. Bulk rhombohedral samples were obtained by solidstate synthesis at high pressure. Mössbauer spectra were analyzed using the model of spatial incommensurate spin-modulated structure of the cycloidal type. Information on the influence of substituting Cr cations for Fe cations on hyperfine spectral parameters was obtained: the shift and quadrupolar shift of a Mössbauer line, and isotropic and anisotropic contributions into the hyperfine magnetic field. The anharmonicity parameter m of the spatial spin-modulated structure increases almost 1.7 times at 5.2 K when BiFeO₃ is doped with chromium. The data on m were used for calculation of the uniaxial magnetic anisotropy constants and their temperature dependences for pure and chromium-doped BiFeO₃.     

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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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⁺.