Spectroscopic properties of Nd<Superscript>3+</Superscript>, Yb<Superscript>3+</Superscript>-doped and Nd<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript>-codoped high silica glass

The Nd³⁺, Yb³⁺-doped and Nd³⁺–Yb³⁺-codoped high silica glasses (HSGs) were fabricated by sintering porous glasses impregnated with Nd³⁺ and Yb³⁺ ions solutions. The Judd–Ofelt theory was used to study the spectroscopic properties of Nd³⁺-doped HSGs. Large parameter Ω₂ of Nd³⁺-doped HSGs suggests a lower centrosymmetric coordination environment around the Nd³⁺ in HSG. The spontaneous emission probability and emission cross-section (σ_em) of Yb³⁺-doped HSGs are obtained. A broad emission band from 950 to 1,100 nm was detected when the Nd³⁺–Yb³⁺-codoped HSG was excited by 808 nm LD. The energy transfer process from Nd³⁺ to Yb³⁺ in HSG was described in this paper.     

Synthesis of Yb<Superscript>3+</Superscript>, Ho<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> co-doped β-NaYF<Subscript>4</Subscript> nanoparticles by sol–gel method and the multi-color upconversion luminescence properties

Well-crystalline β-NaYF₄:Yb³⁺, Ho³⁺, Tm³⁺ nanoparticles were synthesized by sol–gel method using isopropyl alcohol [(CH₃)₂CHOH] as a complexing agent. The samples were characterized by X-ray diffraction, scanning electron microscopic analysis and fluorescence spectrum analysis methods. Under the excitation of 980 nm laser diode (LD), the samples displayed bright upconversion luminescence (UCL), which was generated from the energy level transition of Ho³⁺ and Tm³⁺ ions. With the increase of Tm³⁺, Ho³⁺ and Yb³⁺-doping concentration, the UCL intensity of blue, green and red light emission of the samples varied. Calculation of the CIE color coordinate of the β-NaYF₄:Yb³⁺, Ho³⁺, Tm³⁺ nanoparticles revealed that with the adjustment of Tm³⁺, Ho³⁺ and Yb³⁺ doping concentration and the excitation power of 980 nm LD, the multi-color UCL can be realized. Approximately single red light output with the CIE color coordinate of x?=?0.545, y?=?0.306 and white light output with the CIE color coordinate of x?=?0.325, y?=?0.320 can be obtained in the synthesized β-NaYF₄: Yb³⁺, Ho³⁺, Tm³⁺ nanoparticles.     

Controllable white light emission from Dy<Superscript>3+</Superscript>–Eu<Superscript>3+</Superscript> co-doped KCaBO<Subscript>3</Subscript> phosphor

Potassium calcium borate, KCaBO₃:Eu³⁺ phosphors with various Dy³⁺ concentrations (0–3 wt%) were synthesized by solid state reaction and studied for the first time. Under various UV–violet excitations, the obtained single monoclinic phased Dy³⁺–Eu³⁺ co-doped KCaBO₃ polycrystalline phosphors emit a combination of yellow–blue and red–orange wavelength giving intense white light, which can easily be controlled by varying the concentration of Dy³⁺. The increase in white light emission with the increase of Dy³⁺ concentration indicates the efficient energy inter-ion transfer from Dy³⁺ to Eu³⁺ ions. Furthermore, the observed emission lifetimes and the intense white light emission are suggestive exploration for the present phosphor for potential optoelectronic applications such as white light-emitting phosphor for blue LEDs chips.     

Structure,electrical, and optical properties of ZnO-substituted PbO for the Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–GeO<Subscript>2</Subscript>–Na<Subscript>2</Subscript>O glass system

Glasses of the 0.5Er³⁺/2.5Yb³⁺ co-doped (40Bi₂O₃–20GeO₂–(30 − x)PbO–xZnO–10Na₂O system where x = 0.0, 5, 10, 15, 20, 25, and 30 mol%) have been characterized by FT-IR spectroscopy measurements to obtain information about the influence of ZnO-substituted PbO on the local structure of the glass matrix. The density and the molar volume have been determined. The influences of the ZnO-substituted PbO on the structure of glasses have been discussed. The dc conductivity measured in the temperature range 475–700 K obeys Arrhenius law. The conductivity decreases while the activation energy for conduction increases with increase ZnO content. The optical transmittance and reflectance spectrum of the glasses have been recorded in the wavelength range 400–1100 nm. The values of the optical band gap E _opt for all types of electronic transitions and refractive index have been determined and discussed. The real and imaginary parts ε₁ and ε₂ of dielectric constant have been determined.     

Intense 2.0 µm emission from Ho<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped Na<Subscript>5</Subscript>Lu<Subscript>9</Subscript>F<Subscript>32</Subscript> single crystal excited by 980 nm

This paper reported on optical spectra of Na₅Lu₉F₃₂ single crystals co-doped with ~?0.91 mol% Ho³⁺ and various Yb³⁺ concentrations by using an improved Bridgman method. The emission spectra and fluorescence decay curves were measured to investigate the luminescent properties of the Ho³⁺/Yb³⁺ co-doped Na₅Lu₉F₃₂ and the energy transfer process from Yb³⁺ to Ho³⁺ ion. Compared with the Ho³⁺ singly doped Na₅Lu₉F₃₂ crystal, the Ho³⁺/Yb³⁺ co-doped crystal had an obviously enhanced emission at 2.0 µm via the 980 nm laser diode excitation because of the efficient energy transfer from Yb³⁺ to Ho³⁺ ion. The maximum emission intensity at 2.0 µm was obtained at about 6.99 mol% Yb³⁺ concentration when the concentration of Ho³⁺ ions is fixed at ~?0.91 mol% in the current research. The maximum emission cross section of the above sample at 2.0 µm was calculated to be 1.23?×?10^?20 cm² according to the measured emission spectrum. The energy transfer efficiency from Yb³⁺:²F_5/2 to Ho³⁺:⁵I₆ for the crystal was estimated up to 90.8% indicating that Yb³⁺ ions can efficiently sensitize the Ho³⁺ ions.     

Y<Subscript>2</Subscript>O<Subscript>2</Subscript>S:Er<Superscript>3+</Superscript>,Ce<Superscript>3+</Superscript>—A new “invisible” IR phosphor

Ce³⁺ doping of Y₂O₂S:Er³⁺ can be used to suppress the visible anti-Stokes luminescence of the phosphor under excitation in the range 0.90–0.98 μm. We take advantage of this effect to create a new, efficient “invisible” IR phosphor emitting in the range 1.5–1.6 μm.     

Role of Mg<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript>, and F<Superscript>–</Superscript> ions in octacalcium phosphate crystallization

We have synthesized octacalcium phosphate (OCP) in the presence of inorganic additives (magnesium, strontium, and fluoride ions) and studied the composition, morphology, thermal stability, and dynamic dissolution of the samples thus obtained. It has been shown that, in addition to OCP, magnesium and strontium ions favor the formation of brushite and hydroxyapatite (HA), whereas fluoride ions favor the formation of HA and fluorohydroxyapatite (FHA). We have proposed a process for the preparation of powder materials whose resorption kinetics in corrosive liquid media are corrected by adding dopants capable of activating the dissolution process.     

Sol–gel synthesis of 2D and 3D nanostructured YSZ:Yb<Superscript>3+</Superscript> ceramics

This paper presents results of a detailed study of fundamental aspects of the formation of 2D and 3D nanostructured YSZ:Yb³⁺ ceramics with a cubic structure through a key synthesis step in aqueous solutions of zirconium-containing hydroxy nanoparticles (1–2 nm) modified by Y³⁺ and Yb³⁺ ions, with the use of a sol–gel method and subsequent calcination of the resultant xerogels at temperatures above 350°C. As starting chemicals for the synthesis of ceramic powders, we used zirconyl, yttrium, and ytterbium nitrates and chlorides and aqueous ammonia. Using mixed solutions of these salts and a procedure developed by us, we synthesized sols, gels, and xerogels. To examine the effect of temperature on solid-state transformations, the xerogels were calcined according to a predetermined program in a muffle furnace at temperatures in the range from 350 to 1350°C (rarely, up to 1650°C). We focused primarily on ceramic powders close in composition to 0.86ZrO₂ · 0.10Y₂O₃ · 0.04Yb₂O₃. The ceramics were characterized by high-resolution transmission electron microscopy, electron microdiffraction, electronic diffuse reflectance spectroscopy, energy dispersive X-ray microanalysis, and X-ray fluorescence analysis.     

Luminescent properties of single-phase Ba<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>:Tb<Superscript>3+</Superscript>, R (R = Eu<Superscript>2+</Superscript>, Ce<Superscript>3+</Superscript>) phosphors for white LED

The Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) phosphors were synthesized by use of a co-precipitation method. Crystal phase, excitation and emission spectra of sample phosphors are analyzed by means of XRD and FL, respectively. The emission spectra of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors exhibit four linear peaks attributed to the ⁵D₄?→?⁷F_J (J?=?6–3) transition of Tb³⁺ while four broad emission bands are observed in the emission spectra of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The effects of Eu²⁺ concentration on the luminescent properties of Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) are studied. Ce³⁺ affects the luminescent properties of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors just as the sensitizer. However, Eu²⁺ is considered both as the sensitizer and the activator in Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The chromaticity coordinates of Eu²⁺ and Tb³⁺ co-doped phosphors gather around the white light field with the CCT approximate to 5000 K, indicating that the luminescent property of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors may approach to a desired level needed for white LED application.     

Characterization of <Superscript>4</Superscript>I<Subscript>9/2</Subscript> ↔ <Superscript>4</Superscript>F<Subscript>3/2</Subscript> optical transitions in trivalent Nd<Superscript>3+</Superscript> ions in GaLaS glass

The positions of Stark levels have been determined, using a step-by-step procedure, in the ⁴I_9/2 and ⁴F_3/2 manifolds of Nd³⁺ ions from absorption and photoluminescence measurements in the 12–293 K temperature range. This data has been used to calculate the emission cross-section for which the maximum value turns out to be ～2.3 × 10^?20 cm². The radiative recombination time, calculated using Judd–Ofelt analysis, of the ⁴F_3/2 manifold is in close vicinity to the experimentally determined times that were measured by the conventional decay of PL after interruption of excitation and by QFRS. Moreover, the peak time defined by QFRS is independent of temperature. Therefore, the dominant relaxation mechanism from the ⁴F_3/2 excited manifold of Nd³⁺ ions in GaLaS glass is believed to be by radiative emission.     

Photoluminescence of Eu<Superscript>3+</Superscript> ion in SnO<Subscript>2</Subscript> obtained by sol–gel

Photoluminescence data of Eu-doped SnO₂ xerogels are presented, yielding information on the symmetry of Eu³⁺ luminescent centers, which can be related to their location in the matrix: at lattice sites, substituting to Sn⁴⁺, or segregated at particles surface. Influence of doping concentration and/or particle size on the photoluminescence spectra obtained by energy transfer from the matrix to Eu³⁺ sites is investigated. Results show that a better efficiency in the energy transfer processes is obtained for high symmetry Eu³⁺ sites and low doping levels. Emission intensity from ⁵D₀→⁷F₁ transition increases as the temperature is raised from 10 to 240 K, under excitation at 266 nm laser line, because in this transition the multiphonon emission becomes significant only above 240 K. As an extension of this result, we predict high effectiveness for room temperature operation of Eu-based optical communication devices. X-ray diffraction data show that the impurity excess inhibits particle growth, which may influence the asymmetry ratio of luminescence spectra.     

Synthesis of Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce<Superscript>3+</Superscript> phosphor in the Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al metal–CeO<Subscript>2</Subscript> ternary system

Garnet phosphor Y₃Al₅O₁₂:Ce³⁺ is prepared in the Y₂O₃–Al metal–CeO₂ ternary system by the solid-state reaction method in the air. For the first time, metal Al is used as a source of aluminum for the reaction instead of traditional oxide Al₂O₃. It is shown that the chemical reaction can be realized at lower temperatures and without use of special reducing atmosphere. The structural and spectroscopic properties of the prepared powder phosphor are very close to those earlier reported for the Y₃Al₅O₁₂:Ce³⁺ single crystal.     

Optical properties of Dy<Superscript>3+</Superscript>-doped sodium–aluminum–phosphate glasses

Trivalent dysprosium (Dy³⁺)-doped sodium–aluminum–phosphate (NAP) glasses were prepared and characterized by their optical absorption, excitation, emission spectra, and decay time measurements. Judd–Ofelt intensity parameters were derived from the absorption spectrum and used to calculate the radiative lifetime and stimulated emission cross section of the ⁴F_9/2 → ⁶H_13/2 and ⁴F_9/2 → ⁶H_15/2 transitions. The luminescence intensity ratio of ⁴F_9/2 → ⁶H_13/2 to ⁴F_9/2 → ⁶H_15/2 transitions of Dy³⁺ in NAP glasses gives the feasibility of extracting white light. The lifetime and quantum efficiency of ⁴F_9/2 level is found to be higher than other reported glasses. With increase in Dy³⁺ ion concentration, the decay from ⁴F_9/2 level is found to be faster with decrease in lifetime due to cross relaxation between Dy³⁺ ions.     

Cathodoluminescence properties of SiO<Subscript>2</Subscript>:Pr<Superscript>3+</Superscript>and ZnO·SiO<Subscript>2</Subscript>:Pr<Superscript>3+</Superscript> phosphor nanopowders

The successful incorporation of ZnO nanoparticles in Pr³⁺-doped SiO₂ using a sol–gel process is reported. SiO₂:Pr³⁺ gels, with or without ZnO nanoparticles, were dried at room temperature and annealed at 600 °C. On the basis of the X-ray Diffraction (XRD) results, the SiO₂ was amorphous regardless of the incorporation of Pr³⁺ and nanocrystalline ZnO or annealing at 600 °C. The particles were mostly spherical and agglomerated as confirmed by Field Emission Scanning Electron Microscopy. Thermogravimetric analysis of dried gels performed in an N₂ atmosphere indicated that stable phases were formed at ≥900 °C. Absorption bands ascribed to ³H₄-³P_{(J = 0,1,2)}, ¹I₆ and ¹D₂ in the UV–VIS region were observed from SiO₂:Pr³⁺ colloids. The red cathodoluminescent (CL) emission corresponding to the ³P₀ → ³H₆ transition of Pr³⁺ was observed at 614 nm from dried and annealed SiO₂:Pr³⁺ powder samples. This emission was increased considerably when ZnO nanoparticles were incorporated. The CL intensity was measured at an accelerating voltage of 1-5 keV and a fixed beam current of 8.5 μA. The effects of accelerating voltage on the CL intensity and the CL degradation of SiO₂:Pr³⁺ and ZnO·SiO₂:Pr³⁺ were also investigated using Auger electron spectroscopy coupled with an Ocean Optics S2000 spectrometer.     

Formation-decomposition equilibrium of the NpO<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>·UO<Stack><Subscript>2</Subscript><Superscript>2+</Superscript></Stack> complex in chloride melts

The absorption spectra of the NpO ₂ ⁺ (5f ²) ion were examined in the region of the 3H ₅ ← ³ H ₄ magnetic dipole transition (1530–1760 nm) for series of melts with the UO ₂ ²⁺ concentration varied in the opposite directions: (1) NaCl-2CsCl eutectic melt with growing additions of the Cs₂UO₂Cl₄ complex salt and (2) Cs₂UO₂Cl₄ melt with growing additions of the NaCl-2CsCl mixture. Measurements of the integrated intensities of the bands belonging to the NpO ₂ ⁺ ·UO ₂ ²⁺ complex and unbound NpO ₂ ⁺ throughout the UO ₂ ²⁺ concentration range examined (up to 4.4 M in neat Cs₂UO₂Cl₄ melt) and processing of the data obtained in terms of the mass action law showed that the formation-decomposition reaction of the cation-cation complex can be described adequately only using the equation of reaction in the form NpO₂Cl ₄ ^3? + UO₂Cl ₄ ^2? ? {Cl₄ONpO?UO₂Cl₃}^4? = Cl^? (with the equilibrium constant of 1.3±0.1). Thus, the formation of the cationcation complex should be treated as replacement of chloride ion in the equatorial plane of uranyl(VI) by neptunyl(V), rather than as simple addition of UO ₂ ²⁺ to NpO ₂ ⁺ . The reverse reaction, decomposition of the cation-cation complex, consists essentially in replacement of neptunyl(V) by chloride ion.     

Magnetic and Electrical Properties of Al<Superscript>3+</Superscript> Implanted Co–ZnO

Co-doped ZnO ceramic samples sintered at four different temperatures were prepared by solid-state reaction method and implanted by Al ions subsequently. The microstructural, defect, magnetic and electrical properties of the samples were systematically investigated by x-ray diffraction, micro-Raman spectroscope, vibrating sample magnetometer and Hall measurement, respectively. The results show that all the samples exhibit room-temperature ferromagnetism with a saturation magnetization of 0.02–0.03 emu g^?1, the value of which is affected by the sintering temperature. The origin of room-temperature ferromagnetism is considered as the formation of Co²⁺– V _O–Co²⁺ bound magnetic polarons. Even though the implantation of Al³⁺ slightly reduces the saturation magnetization because of the lattice damage, less V _O and larger lattice spacing, however, an appropriate amount of Al³⁺ implantation and a proper sintering temperature can remarkably improve the electrical properties with the mobility of 200 ～300 cm² Vs^?1 and the resistivity of 20 ～40 Ω cm. In general, samples sintered at 1200^°C present more excellent comprehensive performances.     

The reaction Pu(VI) + Fe(CN)<Stack><Subscript>6</Subscript><Superscript>3−</Superscript></Stack> ⇄ Pu(VII) + Fe(CN)<Stack><Subscript>6</Subscript><Superscript>4−</Superscript></Stack> in NaOH solutions

A spectrophotometric study showed that, in 5 M NaOH, Pu(VII) prepared by ozonation of Pu(VI) is reduced with excess K₄Fe(CN)₆. The Pu(VII) content can be estimated from the amount of the Fe(CN)₆³⁻ formed. In NaOH solutions of concentration exceeding 8 M, the Fe(CN)₆³⁻ ion oxidizes Pu(VI). In 10.3 M NaOH, the tenfold excess of K₃Fe(CN)₆ fully converts 1 mM Pu(VI) to the heptavalent state within 4 min (rate constant 1.3 l mol⁻¹ s⁻¹ at 20°C). With an increase in the NaOH concentration, the oxidation rate increases, and smaller excess of K₃Fe(CN)₆ is required. This oxidant is consumed not only for Pu(VI) oxidation but also in reactions with H₂O and OH⁻ ions. Pu(VII) is unstable and is slowly reduced with water and with products of decomposition of iron complexes.     

Synthesis and photoluminescence characterization of Ce<Superscript>3 + </Superscript> and Dy<Superscript>3 + </Superscript> activated ALa(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>(A = Na and Li) novel phosphors

In this paper, we report the synthesis of Ce^3 + and Dy^3 + activated alkali lanthanide tungstates, ALa(WO₄)₂(where A = Na and Li), prepared by solid state reaction method. The prepared phosphors were characterized by X-ray diffraction and photoluminescence techniques. The NaLa(WO₄)₂:Dy^3 + and LiLa(WO₄)₂:Dy^3 + phosphors show two emission peaks at around 574 and 486 nm (λ_exc = 354 nm). NaLa(WO₄)₂:Ce^3 + and LiLa(WO₄)₂:Ce^3 + show two emission peaks at around 378 and 425 nm (λ_exc = 350 nm). Excitation wavelengths of Ce^3 + and Dy^3 + activated alkali lanthanide tungstates are in near UV region i.e. Hg free excitation. These characterizations of phosphors are applicable for solid state lighting. Accordingly, Ce^3 + and Dy^3 + activated NaLa(WO₄)₂ and LiLa(WO₄)₂ may be the promising materials for solid state lighting applications.     

Ho<Superscript>3+</Superscript>-Doped ZrF<Subscript>4</Subscript>–BaF<Subscript>2</Subscript>–BiF<Subscript>3</Subscript> Ceramic 2-µm laser beam visualizer

A ceramic 2-µm laser beam visualizer based on Ho³⁺-doped β-BaZrF₆ is proposed. The ceramic has been prepared by crystallizing 60ZrF₄–35BaF₂–5BiF₃ glass doped with 3 wt % HoF₃. Exciting the Ho³⁺⁵I₇ level by a Tm:LiYF₄ (Tm:YLF) laser at λ = 1910 nm, we observed a strong red luminescence, due to the ⁵F₅ → ⁵I₈ transition, and a weaker, green luminescence, corresponding to the (⁵F₄, ⁵S₂) → ⁵I₈ transition. The threshold power density of the Tm:YLF laser at which a red spot was observed on a ceramic sample was 1.1 W/cm².     

Distribution of <Superscript>210</Superscript>Ро in lichen thalli

Distribution of ²¹⁰Po in thalli of soil and wood (epiphytic) lichens was studied. Four fractions containing the corresponding ²¹⁰Ро forms were obtained by sequential extraction: (1) intercellular, (2) extracellular, (3) intracellular, and (4) insoluble thallus residue. The ²¹⁰Ро uptake by lichens is mainly passive, as the total content of the radionuclide in fractions 1, 2, and 4 reaches 88–97%. From 3 to 12% of ²¹⁰Ро is taken up actively (fraction 3), and for soil lichens this parameter is approximately 2.75 times higher than for epiphytic lichens. Presumably, ²¹⁰Ро is supplied into soil and epiphytic lichens in the form of different chemical compounds and is therefore characterized by different bioavailability.