Hydrothermal synthesis of core-shell structured PS@GdPO<Subscript>4</Subscript>:Tb<Superscript>3+</Superscript>/Ce<Superscript>3+</Superscript> spherical particles and their luminescence properties

Non-aggregated spherical polystyrene (PS) particles were coated with GdPO₄:Tb³⁺/Ce³⁺ phosphor layers by a conventional hydrothermal synthesis using poly(vinylpyrrolidone) (PVP) as an additive without further annealing treatment. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL), as well as luminescence decay experiments were used to characterise the resulting core-shell structured PS@GdPO₄:Tb³⁺/Ce³⁺ samples. The results of XRD indicated that the PS particles were successfully coated with the GdPO₄:Tb³⁺/Ce³⁺ phosphor layers, which could be further verified by the images of FESEM. Under ultraviolet excitation, the PS@GdPO₄:Tb³⁺/Ce³⁺ phosphors show Tb³⁺ characteristic emission, i.e. ⁵D₄-⁷F_J (J = {6, 5, 4, 3}) emission lines with green emission ⁵D₄-⁷F₅ (543 nm) as the most prominent group. The core-shell phosphors so obtained have potential applications in field emission display (FED) and plasma display panels (PDP).     

Photocatalysis enhancement of CaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, Nd<Superscript>3+</Superscript>@TiO<Subscript>2</Subscript> composite powders

CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders were synthesized by a sol–gel method under mild conditions (i.e. low temperature and ambient pressure). The as-prepared powders were characterized by transmission electron microscopy (TEM) and analyzed by X-ray diffraction (XRD). The photocatalytic behavior of the TiO₂-base surfaces was evaluated by the degradation of nitrogen monoxide gas. It suggested that CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders were composed of anatase titania and that CaAl₂O₄:Eu²⁺, Nd³⁺. TiO₂ particles were deposited on the surface of CaAl₂O₄:Eu²⁺, Nd³⁺ to form uniform film. CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders exhibited higher photocatalytic activity compared with pure TiO₂ under visible light. And the result also clearly indicated that the long afterglow phosphor absorbed and stored lights for the TiO₂ to remain photocatalytic activity in the dark.     

A new phosphor with flower-like structure and luminescent properties of Sr<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>: Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript> long afterglow materials by sol–gel method

The flower-like phosphors of Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ with high brightness and long afterglow were obtained by sol–gel method. X-ray diffraction pattern (XRD) shows that single-phased Sr₂MgSi₂O₇ phosphor is prepared by sol–gel method under 1250 °C. Scanning electron microscope (SEM) indicates that the phosphor consists of nano-sized whiskers which are detected for the first time in Eu²⁺ and Dy³⁺ co-doped long-lasting phosphorescence silicates. Furthermore, the investigation on the mechanism indicates that the internal structure and gas, liquid and solid phase effect play important roles in the formation of flower-like Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ nanostructure. Finally, the optical properties of flower-like Sr₂MgSi₂O₇ nanostructure have been characterized by photoluminescence (PL) spectra.     

Flame synthesized Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Tb<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript> phosphors as spectral convertors for solar cells

Near-infrared (NIR) quantum cutting phosphors serve as a potential material for fabricating photovoltaic spectral convertors. In many cases, quantum cutting phosphors are obtained via a wet chemical method coupled with a post-annealing treatment—a very costly process. In this report, we used continuous flame spray pyrolysis (FSP) for fabricating Y₂O₃:Tb³⁺–Yb³⁺ quantum-cutting phosphors without any post-treatment. Based on characterizations by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, we found that as-synthesized Y₂O₃:Tb³⁺–Yb³⁺ phosphors exhibit hollow and shell-like micro-structures composed of highly crystalline and pure cubic-phase nanoparticles (< 50 nm). Photoluminescence studies of the phosphors revealed that NIR emissions appeared with the introduction of Yb to Y₂O₃:Tb³⁺. Phosphor size was successfully controlled by managing the concentration of the metal precursor solution for FSP. The Y₂O₃:Tb³⁺–Yb³⁺ phosphors were then embedded into transparent poly-ethylene-co-vinyl acetate (EVA) film to form a spectral convertor. The composite films of Y₂O₃:Tb³⁺–Yb³⁺ phosphors and poly-EVA were found to be highly transparent in the visible range (> 500 nm), making them suitable as spectral photovoltaic convertors.     

Enhancement of the photoluminescence and long afterglow properties of Ca<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>2+</Superscript> phosphor by Dy<Superscript>3+</Superscript> co-doping

The Ca₂MgSi₂O₇:Eu²⁺ and Ca₂MgSi₂O₇:Eu²⁺, Dy³⁺ long afterglow phosphors were synthesized under a weak reducing atmosphere by the traditional high temperature solid state reaction method. The synthesized phosphors were characterized by powder X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX) techniques. The luminescence properties were investigated using thermoluminescence (TL), photoluminescence (PL), long afterglow, mechanoluminescence (ML), and ML spectra techniques. The crystal structure of sintered phosphors was an akermanite type structure, which belongs to the tetragonal crystallography. TL properties of these phosphors were investigated, and the results were also compared. Under the ultraviolet excitation, the emission spectra of both prepared phosphors were composed of a broad band peaking at 535 nm, belonging to the broad emission band. When the Ca₂MgSi₂O₇:Eu²⁺ phosphor is co-doped with Dy³⁺, the PL, afterglow and ML intensity is strongly enhanced. The decay graph indicates that both the sintered phosphors contain fast decay and slow decay process. The ML intensities of Ca₂MgSi₂O₇:Eu²⁺ and Ca₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors were proportionally increased with the increase of impact velocity, which suggests that this phosphor can be used as sensors to detect the stress of an object.     

UV excited green luminescence of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript> nanophosphor

Eu, Dy co-doped strontium aluminate nanophosphors were prepared by the combustion synthesis method. Their structure and morphology were investigated by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy. According to the XRD and the TEM analysis, the average crystallite size was found to be in the nanometer range. The phase structure of the prepared nanophosphor is consistent with a standard monoclinic phase with a space group P2₁. The prepared SrAl₂O₄:Eu²⁺, Dy³⁺ nanophosphor emitted green light with a peak at 510 nm showing blue shift, which is due to the reduction in the particle size. Two distinct peaks were observed in the ML intensity versus time curve. The two peaks in ML indicate the presence of charge transfer in an ML process.     

Detection of up-conversion in nano-structure BaTiO<Subscript>3</Subscript> co-doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> ions

Nano-structure pure barium titanate BaTiO₃ (BT) and (BT) co-doped with constant concentration of Er³⁺ ions and different concentrations of Yb³⁺ ions were prepared using sol–gel method. XRD results confirmed that the pure sample was found to crystallize in tetragonal phase by sintering at 750 °C for 1 h. All major peaks corresponding to perovskite BT phase appeared. Efficient infrared-to-visible up-conversion is reported in the doped samples. The conversion process and results in the generation of visible emissions are discussed. Up-conversion efficiency for red emission predominates in doped samples. Results illustrate the large potential of this class of materials for photonic applications in optoelectronics devices.     

Water-soluble polymers as chelating agents for the deposition of Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>:LiNbO<Subscript>3</Subscript> waveguiding films

Compared to other oxide materials, the sol-gel deposition of an optically transparent LiNbO₃ waveguiding film of sufficient thickness (approx. 1?μm) is complicated by the presence of a highly hydrolyzing Nb(V) in the starting solution. Thicker films require more concentrated solutions that are not easily achieved for such ions. This problem may be solved using strong chelating agents such as water-soluble polymers. To prepare a stable Er(III)/Yb(III)/Li(I)/Nb(V)/2-methoxyethanol solution with high metal concentration, we tested three such polymers: polyethylene glycol (PEG), polyacrylic acid (PAA) and polyvinyl alcohol (PVA), and compared them with already used polyvinylpyrrolidone (PVP). The solutions were spin-coated on crystalline sapphire substrates under a multi-step heating-deposition regime. Apart from Er³⁺/Yb³⁺ photoluminescence properties, we evaluated the influence of the film microstructure (SEM, AFM) on optical transparency and waveguiding ability in the UV/Vis/NIR region (transmission and m-line spectroscopy). Among the newly tested polymers, only PEG was able to prevent Nb(V) hydrolysis up to a maximum metal concentration of 0.6?mol/L. For PEG and PVP, the crystallization temperature of the deposited films (between 700?°C and 1000?°C) was compared. After further optimization of the heating-deposition process, we were able to prepare a transparent Er³⁺/Yb³⁺:LiNbO₃ film thick enough to guide an optical signal in the NIR region. Thus, the use of PEG results is one of the very few non-hydrolytic sol-gel methods suitable for the preparation of not only luminescent, but also waveguiding Er³⁺/Yb³⁺:LiNbO₃ structures.

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Two color up-conversion emissions of Er<Superscript>3+</Superscript>-doped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanopowders prepared by non-aqueous sol-gel method

Er³⁺-doped Al₂O₃ nanopowders have been prepared by the non-aqueous sol-gel method using the aluminum isopropoxide as precursor, acetylacetone as a chelating agent, nitric acid as a catalyzer, and hydrated erbium nitrate as a dopant under isopropanol environment. The different phase structure, including three crystalline types of (Al, Er)₂O₃ phases, α, γ, θ, and an Er–Al–O stoichiometric compound phase, Al₁₀Er₆O₂₄, was observed for the 0.01–0.5 mol% Er³⁺-doped Al₂O₃ nanopowders at the sintering temperature of 1,000 °C. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the ²H_11/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺, were detected by a 978 nm semiconductor laser diodes excitation. With increasing Er³⁺ doping concentration from 0.01 to 0.1 mol%, the intensity of the green and red emissions increased with a decrease of the intensity ratio of the green to red emission. When the Er³⁺ doping concentration rose to 5 mol%, the intensity of the green and red emissions decreased with an increase of their intensity ratio. The maximum intensity of both the green and red emissions with the minimum of intensity ratio was obtained, respectively, for the 0.1 mol% Er³⁺-doped Al₂O₃ nanopowders composed of a single α-(Al,Er)₂O₃ phase. The intensity ratio of the green emission at 523 and 545 nm increased monotonously for all Er³⁺ doping concentrations. The two-photon absorption up-conversion process was involved in the green and red up-conversion emissions of the Er³⁺-doped Al₂O₃ nanopowders.     

Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> phase diagram

Phase relations in the Y₂O₃-Ga₂O₃ system were studied by the anneal-and-quench technique in air within 1000–2300°C, and a phase diagram was plotted. Three compounds were found to form: Y₃GaO₆, Y₄Ga₂O₉, and Y₃Ga₅O₁₂; the temperature and concentration bounds of stability were determined for these compounds. Indexing results for Y₃GaO₆ are given.     

Optical energy storage properties of Sr<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>2+</Superscript>,R<Superscript>3+</Superscript> persistent luminescence materials

The details of the mechanism of persistent luminescence were probed by investigating the trap level structure of Sr₂MgSi₂O₇:Eu²⁺,R³⁺ materials (R: Y, La-Lu, excluding Pm and Eu) with thermoluminescence (TL) measurements and Density Functional Theory (DFT) calculations. The TL results indicated that the shallowest traps for each Sr₂MgSi₂O₇:Eu²⁺,R³⁺ material above room temperature were always ca. 0.7 eV corresponding to a strong TL maximum at ca. 90 °C. This main trap energy was only slightly modified by the different co-dopants, which, in contrast, had a significant effect on the depths of the deeper traps. The combined results of the trap level energies obtained from the experimental data and DFT calculations suggest that the main trap responsible for the persistent luminescence of the Sr₂MgSi₂O₇:Eu²⁺,R³⁺ materials is created by charge compensation lattice defects, identified tentatively as oxygen vacancies, induced by the R³⁺ co-dopants.     

Synthesis and characterization of Eu<Superscript>3+</Superscript> doped Lu<Subscript>2</Subscript>O<Subscript>3</Subscript> nanophosphor using a solution-combustion method

Fine Eu³⁺-doped lutetium oxide (Lu₂O₃:Eu³⁺) nanophosphor were synthesized using a low-temperature solution-combustion method in a methyl-alcohol solution. The characteristics of the nanophosphors synthesized at various sintering temperatures with different Eu³⁺ concentrations were analyzed to determine the optimum synthesis conditions. Thermogravimetry/differential thermal analysis showed that Lu₂O₃:Eu³⁺ crystallizes completely when the dry powder is sintered at 500 °C. The Lu₂O₃:Eu³⁺ crystals had a cubic structure and monoclinic phase. The peak position of the luminescence spectrum did not differ with the concentration of Eu or the sintering temperature or atmosphere, whereas the luminescence intensity was strongly dependent on the concentration and sintering conditions.     

Synthesis and electrochemical properties of yttrium-doped LiMn<Subscript>0.98</Subscript>Y<Subscript>0.02</Subscript>O<Subscript>2</Subscript> for lithium secondary batteries

Yttrium-doped lithium manganese oxide (LiMn_0.98Y_0.02O₂) was prepared by ion exchange of lithium for sodium in NaMn_0.98Y_0.02O₂ precursors obtained by using rheological phase reaction method. This material had small particle size, which was composed of grain size of about 100 nm. Especially, LiMn_0.98Y_0.02O₂ delivered the initial discharge capacity of about 191 mA h g⁻¹ at room temperature when cycled between 2.0 and 4.4 V vs Li/Li⁺. Moreover, it showed an excellent cycling behavior, its specific capacity remained above 173 mA h g⁻¹ after 20 cycles, and the material did not transform into spinel structure during the electrochemical cycling according to the cyclic voltammograms and X-ray powder diffraction. The electrochemical results revealed that the doping of Y³⁺ improved the performance of LiMnO₂ considerably.     

EPR and optical study of coupled Yb<Superscript>3+</Superscript> ion pairs in weakly doped LiNbO<Subscript>3</Subscript>:Yb single crystal

The results of electron paramagnetic resonance and optical spectroscopy studies of Yb³⁺ ions in LiNbO₃:1% Yb host crystal are reported. Also some results of Raman spectra measurements are presented. The observed features are assigned to single Yb³⁺ ions and pairs of dissimilar ions (with different g value) of the type of ^evenYb³⁺-^evenYb³⁺. The values of the components of the g-tensor for both ions and interaction exchange tensors are estimated. The value of J = ?0.0283 cm^?1 shows that the exchange interactions are of antiferromagnetic nature. The most probably the ^evenYb³⁺-^evenYb³⁺ pairs substitute for neighborhood Li⁺-Nb⁵⁺ positions what induces gain of distance between ions of about 1 Å. There are no observed dissimilar ion pairs of the type ^oddYb³⁺-^oddYb³⁺.     

Effects of boric acid on structural and luminescent properties of BaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:(Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript>) phosphors

Eu²⁺/Dy³⁺-codoped BaAl₂O₄ phosphors were prepared by conventional solid-state reaction with boric acid flux. The effects of boric acid on structural and luminescent properties of BaAl₂O₄:(Eu²⁺, Dy³⁺) were investigated. The crystallinity of BaAl₂O₄ improved with increasing amount of H₃BO₃. Incorporation of Eu²⁺ and Dy³⁺ ions into effective lattice sites was promoted by H₃BO₃ addition. As a result, Eu²⁺ emission in BaAl₂O₄ was greatly enhanced by H₃BO₃, and the duration of persistent luminescence increased with the amount of H₃BO₃. However, the decay lifetime of persistent luminescence was not strongly influenced by the amount of H₃BO₃.     

Magneto-optic and luminescent properties of tellurite glass TeO<Subscript>2</Subscript>-ZnCl<Subscript>2</Subscript> doped with rare-earth elements

Tellurite glasses were synthesized on the basis of the binary system composed of 70 mol % TeO₂ and 30 mol % ZnCl₂ and doped with Nd³⁺, Pr³⁺, Tb³⁺, Er³⁺, Yb³⁺, Ho³⁺. The physicochemical, luminescent, and magneto-optic properties of these glasses were studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1262–1265.Original Russian Text Copyright © 2004 by Grishin, Gurev, Intyushin, Elliev, Pavlova, Savikin.     

Eu<Superscript>3+</Superscript>-fluorescence properties in nano-crystallized SnO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript> glass-ceramics

Fluorescence and spectral hole burning properties of Eu³⁺ ions were studied in nanocrystals-precipitated SnO₂-SiO₂ glasses. The glasses were prepared to contain various amount of Eu₂O₃ using the sol-gel method, in which SnO₂ nanocrystals were precipitated by heating in air. In the glasses containing Eu₂O₃ less than 1%, the Eu³⁺ ions were preferentially doped in the SnO₂ nanocrystals and their fluorescence intensities were enhanced by the energy transfer due to the recombination of electrons and holes excited in SnO₂ crystals. The SnO₂ nanocrystals-precipitated glasses exhibited the persistent spectral holes with the depth of ∼25% of the total fluorescence intensities of the Eu³⁺ ions. With the increasing Eu₂O₃ concentration, the amount of SnO₂ nanocrystals decreased and the Sn⁴⁺ ions formed the random glass structure together with the silica network. This structure change induced the fluorescence intensities and the hole depth to decrease.     

Yttria stabilized zirconia solid electrolyte surface modification with ZrO<Subscript>2</Subscript>, Y<Subscript>2</Subscript>O<Subscript>3</Subscript>, and ZrO<Subscript>2</Subscript> + 9 mol % Y<Subscript>2</Subscript>O<Subscript>3</Subscript> films

The surface of ceramic electrolyte ZrO₂ + 9 mol % Y₂O₃, hereinafter referred to as YSZ (abbreviated yttria stabilized zirconia), was modified with 0.1 to 0.2 μm oxide films of ZrO₂, Y₂O₃, and YSZ (same composition as substrate) by dip coating in alcohol solutions of the relevant salts and further annealing. The results of scanning electronic microscopy and X-ray diffraction evidence epitaxial film growth. By means of impedance spectroscopy at the temperatures of 500 to 600°C, the effect of YZS electrolyte surface modification with ZrO₂, Y₂O₃, and YSZ films to the polarization resistance of silver electrode was studied.     

Photoluminescence in Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>-doped silica-titania inverse opal structures

Er³⁺ photoluminescence (PL) and Yb³⁺ → Er³⁺ energy transfer (ET) phenomena in the near infrared (NIR) have been studied in three-dimensional (3-D) inverse opal (IO) structures synthesized by a colloidal/sol–gel route, starting with the deposition of polystyrene microsphere (235 nm and 460 nm diameter) direct opal templates by convective self-assembly, followed by infiltration of the interstices with Er³⁺/Yb³⁺-doped silica, titania and silica-titania sols and heat-removal of the polymeric template material. The crystalline quality of the IOs has been optimized through suitable substrate treatments, plus the control of temperature and humidity during deposition of the templates. The structural and optical properties of the 3-D opal and IO structures have been studied by field emission scanning electron microscopy and visible-NIR reflection spectroscopy, in order to assess the relationship between microstructure and the photonic properties obtained. Photonic bandgaps have been evidenced by the corresponding stop bands in the reflection spectra. The shape and the intensity of the Er^{3+ 4}I_13/2 → ⁴I_15/2 transition at ~1.5 μm were modified in most IOs relatively to similar matrix deposits without a photonic crystal structure, particularly in the case of pure silica and titania IOs, where the PL peak narrowed and intensified. It was not possible at this stage to detect Yb³⁺ → Er³⁺ ET phenomena in the IOs structures.     

Study of Complex Formation between Kryptofix 21 with La<Superscript>3+</Superscript>, Y<Superscript>3+</Superscript> and Ce<Superscript>3+</Superscript> Cations in Some Binary Mixed Non-Aqueous Solvents Using the Conductometric Method

The complexation reactions between La³⁺, Y³⁺ and Ce³⁺ cations with the macrocyclic ligand, kryptofix 21, were studied in methanol-acetonitrile (MeOH-AN) and methanol-methylacetate (MeOHMeOAc) binary mixed solvent solutions at different temperatures using the conductometric method. The conductance data show that in most solvent systems, the kryptofix 21 forms a 1: 1 [M: L] complex with La³⁺, Y³⁺ and Ce³⁺ metal cations, but in the case of Y³⁺ cation in pure methylacetate, in addition of formation of a 1: 1 [ML] complex, 1: 2 [ML₂] and 1: 3 [ML₃] complexes are formed in solution. In the case of Ce³⁺cation, a 1: 1 [ML] and also a 1: 2 [ML₂] complexes are formed in this solvent system at all studied temperatures. The electrical conductance data in acetonitrile, show that a 1: 1 [ML] and also a 1: 2 [ML₂] complexes are formed between the ligand and La³⁺ and Ce³⁺ metal cations at different temperatures. The stability constants of the 1: 1 [ML] complexes were determined using the conductometric data and a computer program, GENPLOT. A non-monotonic relationship was observed between log_{K f} of the 1: 1 complexes with the composition of the binary solvent solutions which was discussed in term of solvent-solvent interactions and also preferential solvation of the metal cations and the ligand in solutions. The selectivity order of the ligand for the metal cations in MeOH–AN and MeOH–MeOAc binary solvent solutions, at 25°C was found to be: Y³⁺ > La³⁺ > Ce³⁺ and La³⁺ > Y³⁺ > Ce³⁺, respectively. The values of the standard thermodynamic quantities (ΔH _c ^° and ΔS _c ^° ) for formation of the 1: 1 complexes were obtained from temperature dependence of the stability constans of the complexes and the results show that the thermodynamics of the complexation reactions between kryptofix 21 and La³⁺, Y³⁺ and Ce³⁺ cations, is affected by the nature and composition of the mixed solvents systems.