Nanostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles: polyol-mediated synthesis and luminescent properties

Nano-submicrostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles were prepared by polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), photoluminescence (PL), cathodo-luminescence (CL) spectra and PL lifetimes. The results of XRD indicate that the as-prepared samples are well crystallized with the scheelite structure of CaWO4. The FE-SEM images illustrate that CaWO4 and CaWO4 : Pb2+ and CaWO4 : Tb3+ powders are composed of spherical particles with sizes around 260, 290, and 190 nm respectively, which are the aggregates of smaller nanoparticles around 10-20 nm. Under the UV light or electron beam excitation, the CaWO4 powders exhibits a blue emission band with a maximum at about 440 nm. When the CaWO4 particles are doped with Pb2+, the intensity of luminescence is enhanced to some extent and the luminescence band maximum is red shifted to 460 nm. Tb(3+)-doped CaWO4 particles show the characteristic emission of Tb3+ 5D4-7FJ (J = 6 - 3) transitions due to an energy transfer from WO4(2-) groups to Tb3+.     

Patterning of red, green, and blue luminescent films based on CaWO4:Eu3+, CaWO4:Tb3+, and CaWO4 phosphors via microcontact printing route

The multicolor patterned luminescent films of CaWO(4):Eu(3+) (red), CaWO(4):Tb(3+) (green), and pure CaWO(4) (blue) on quartz substrates were fabricated by the facile and low-cost microcontact printing (μCP) method combining with the Pechini sol-gel route. On the basis of the μCP process, a hydrophobic self-assembled monolayer (SAM) was first created on the hydrophilic surface of quartz substrates by poly(dimethylsiloxane) (PDMS) mold printing, and then, the multicolor patterned luminescent films were selectively deposited on the hydrophilic regions via a spin coating process and heating treatment. The X-ray diffraction, optical microscopy, scanning electron microscopy, and photoluminescence (PL) spectra were used to characterize the structure and fluorescence properties of the corresponding samples. The results demonstrate that the μCP process can be used for patterning the inorganic phosphor materials and have potential for fabricating rare-earth luminescent pixels for the applications of display devices.     

燃烧法合成CaMoO4∶Eu3+及其发光性能的研究

采用柠檬酸作为燃料,通过燃烧法制备了CaMoO4蓝色以及CaMoO4:Eu3+红色荧光粉.研究了Eu3+的掺入、反应温度以及反应时间对所制得的CaMoO4:Eu3+的晶体结构以及发光性能的影响.XRD谱图分析显示合成样品CaMoO4和CaMoO4:Eu3+均为白钨矿型晶体结构,晶体的结晶度随着合成温度的升高以及保温时间...     

Hydrothermal synthesis and luminescent properties of GdVO4 : Eu3+ nanophosphors

Eu³⁺-doped GdVO₄ has been synthesised via hydrothermal method by altering the hydrothermal temperature, reaction time and surfactant. The microstructure and morphology information of the phosphors were investigated via the techniques of X-ray powder diffraction and scanning electronic microscopy, which show that the phosphors wear tetragonal phase and the products present various regular morphologies under different reaction conditions such as bulk and nanoparticle. Moreover, the morphologies of the products have been controlled by altering reaction temperature. In addition, the surfactant was also included to control the morphologies of the products and the phosphors present different morphologies. All the phosphors exhibit the characteristic fluorescence of Eu ion (⁵D₀ → ⁷F₂ and ⁵D₀ → ⁷F₂). The electric dipole transition ⁵D₀ → ⁷F₂ of Eu³⁺ is dominant indicating that most sites of Eu³⁺ ions in GdVO₄ have no inversion centre. Furthermore, we found that the reaction time and the morphologies have great influence on optical properties.     

Synthesis and luminescent properties of spindle-like CaWO4:Sm3+ phosphors

Spindle-like CaWO₄:Sm³⁺ phosphors were prepared via a Polyvinylpyrrolidone (PVP)-assisted sonochemical process, and characterized by using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and photoluminescence spectroscopy (PL). The XRD results suggested that the prepared samples are single-phase. The FE-SEM images indicated that the prepared CaWO₄:Sm³⁺ phosphors are composed of many spindles with maximum average diameter of 150 nm and maximum average length of 500 nm. Under 404 nm excitation, the characteristic emissions corresponding to ⁴G_5/2 → ⁶H_J (J = 5/2, 7/2, 9/2 and 11/2) transitions of Sm³⁺ in CaWO₄ phosphors were observed. The color coordinates for 1 mol% Sm³⁺ doped CaWO₄ phosphor were calculated to be (0.595, 0.404). The fluorescent concentration quenching of Sm³⁺ doped spindle-like phosphors was studied based on the Van Uitert's model, and it was found that the electric dipole–dipole (D–D) interaction is the dominant energy transfer mechanism between Sm³⁺ ions in the CaWO₄:Sm³⁺ phosphors. The critical energy transfer distance was estimated.     

One-step synthesis and luminescent properties of nanocrystalline YVO4:Eu3+ powders

In this paper, nanocrystalline YVO4:Eu3+ powders have been successfully synthesized via high-temperature solution-phase synthesis process. The nanocrystalline YVO4:Eu3+ particles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV/Nis absorption spectra and luminescence spectra, luminescence decay curve and Fourier transform infrared (FT-IR), X-ray photoelectron spectra (XPS) respectively. The as-prepared nanocrystalline YVO4:Eu3+ particles are well crystallized with ellipsoidal morphology. The emission of YVO4:Eu3+ particles show emission originating from the 5D0 level, with 5D0-7F2 at 616 nm as the most prominent group. The excitation spectrum fits basically with the absorption spectrum from the vanadate ions. FT-IR and XPS spectra indicate that the surface ligands of nanocrystalline particles were oleic acid and oleylamine. The lifetime for the luminescence of Eu3+ in the as-prepared YVO4:Eu3+ samples are shorter than that of the bulk material due to the absorption of organic ligands on the nanoparticle surface.     

Molten salt synthesis,characterization, and luminescence of SrWO4, SrWO4:Tb3+ and SrWO4:Eu3+ powders

SrWO₄, SrWO₄:Tb³⁺, and SrWO₄:Eu³⁺ powders were synthesized by a method of molten salt. XRD patterns showed that the synthesized powders have a pure tetragonal scheelite structure without the presence of deleterious phases. Scanning electron microscopy images show that powders are in the range of 20–35 nm. The emission spectrum of SrWO₄ shows the emission peak in the blue spectral region. The excitation spectra of SrWO₄:Tb³⁺ and SrWO₄:Eu³⁺ show the energy transfer from WO₄ ^2? group to Tb³⁺ and Eu³⁺ ions with a high efficiency. The emission spectrum of SrWO₄:Tb³⁺ shows the green emission at 545 nm corresponding to the ⁵D₄ → ⁷F₅ transition of Tb³⁺. The emission spectrum of SrWO₄:Eu³⁺ shows the red emission located at 612 nm corresponding to the ⁵D₀ → ⁷F₂ transition of Eu³⁺. The asymmetry ratio of SrWO₄:Eu³⁺ is found to be 5.54, which indicates that the Eu³⁺ ions are located in a lower symmetric site.     

Influence of Zn2+ and Si4+ codoping on luminescence properties of CaWO4:Eu3+ phosphor

The red afterglow phosphors of CaWO₄ doped with Eu³⁺, Zn²⁺ or (and) Si⁴⁺ were prepared by solid state reaction. All crystalline phases were identified by the X-ray powder diffraction (XRD). The photoluminescence spectra and decay curves as well as thermoluminecence (TL) curves of all samples were also investigated. In comparison to CaWO₄:Eu³⁺ phosphor, the luminescence and afterglow properties could be improved greatly after being doped with Zn²⁺ or (and) Si⁴⁺ ions.     

Preparation and luminescent properties of YVO4:Eu3+ nanofibers by electrospinning

This paper describes a procedure based on electrospinning for generating europium-doped yttrium vanadate (YVO4:Eu3+) nanofibers with diameters ranging from 30 to 50 nm. The YVO4:Eu3+ nanofibers were obtained through calcining precursory nanofibers, which were prepared through the electrospinning method. Suitable electrospinning parameters, such as concentration of PVP in solution, spinneret tip-to-collector plate distance (TCD), and applied voltage between spinneret and collector plate, are used to obtain thinner and more uniform precursory nanofibers of YVO4:Eu3+, which is important for preparing smaller diameter pure YVO4:Eu3+ nanofibers. The luminescent properties of the YVO4:Eu3+ nanofibers including excitation and emission spectra and fluorescence lifetime were studied. The excitation spectrum shows a broad band extending from 200 to 350 nm, which corresponds to the strong vanadate absorption in YVO4:Eu3+. The emission spectrum is dominated by the red 5D0 --> 7F2 hypersensitive transition of Eu3+. The fluorescence lifetime of Eu3+ 5D0 --> 7F2 (619 nm) is determined to be 493 micros at room temperature, which is basically in accordance with that in the bulk (521 micros).     

Branch-shaped NaGdF4:Eu3+ nanocrystals: Selective synthesis,and photoluminescence properties

The branch-shaped NaGdF₄:Eu³⁺ nanocrystals (NCs) were synthesized by using polyvinylpyrrolidone (PVP) as a capping agent in ethylene glycol (EG) solution. The NCs were readily dispersed into water or ethanol to form a relatively stable suspension, which may facilitate their applications in biological fields. Meanwhile, the crystal structures of the NCs were tunable from the mixture of the α-(cubic) and β-(hexagonal) phases to the pure β-phase by varying the F^?/Ln³⁺ molar ratio or the reaction temperature. The pure β-phase NCs were obtained at relatively high F^?/Ln³⁺ molar ratio and reaction temperature. In addition, the Eu³⁺-doping concentration—dependent optical properties of the NaGdF₄:Eu³⁺ NCs were investigated in detail. The result shows that the emissions from high energy level transitions (e.g., ⁵D₁, ⁵D₂, and ⁵D₃) are significantly impaired with increasing the Eu³⁺-doping concentration due to the cross-relaxation process, and the emission at 612 nm is predominant since the doped Eu³⁺ ions locate in the crystal fields without inversion center.     

Magnetic and luminescent properties of Fe3O4@Y2O3:Eu3+ nanocomposites

The multifunctional Fe₃O₄@Y₂O₃:Eu³⁺ nanocomposites were prepared by a facile solvothermal method with Fe₃O₄ nanoparticles as the core and europium-doped yttrium oxide (Y₂O₃:Eu³⁺) as the shell. It is shown that Fe₃O₄@Y₂O₃:Eu³⁺ nanocomposites have a strong photoluminescence and special saturation magnetization Ms of 6.1 emu/g at room temperature. The effects of the magnetic field on the luminescence intensities of the nanocomposites are being discussed. The multifunctional nanocomposites with magnetic resonance response and fluorescence probe properties may be useful in biomedical applications, such as cell separation and bioimaging.     

Effects of pressure on the emission of CaWO4:Eu3+ phosphor

CaWO₄:Eu³⁺ (Ca_0.925Eu_0.05WO₄) and CaWO₄ phosphors were synthesized by solid state method. Here, the pressure effect on the photoluminescence of CaWO₄:Eu³⁺ has been investigated with a diamond anvil cell up to 20 GPa at room temperature. It is observed that pressure has a great influence on the fluorescence intensity and the energy levels. With increasing pressure, the spectral features shift towards lower energies, and the ⁷F₁ multiplet will split into three Stark levels due to the removal of the degeneracy by the crystal-field interaction. In addition, the emission intensity of the ⁵D₀ → ⁷F₁ transition decreases significantly. Raman experiments further confirm the scheelite to wolframite structure transformation presents at around 10 GPa. Upon release of pressure, this high-pressure phase transforms back to the original scheelite phase, and continuously remains stable to ambient conditions.     

Preparation and luminescent properties of doped with Eu3+ ions YVO4 nanophosphors

YVO₄:Eu³⁺ nanophosphors were prepared by a sol–gel method. The structure and luminescent properties of YVO₄:Eu³⁺ nanophosphors are characterized by XRD and luminescent spectrophotometer. There are excellent luminescent properties for YVO₄:Eu³⁺ nanophosphors. The nanophosphors are applied in bioapplications field.     

Highly uniform NaLa(MoO4)2:Eu3+ microspheres: microwave-assisted hydrothermal synthesis,growth mechanism and enhanced luminescent properties

Uniform and well-crystallized NaLa(MoO₄)₂ microspheres were prepared by a facile microwave-assisted hydrothermal method at low temperature without any surfactants or templates. The as-prepared products were systematically characterized by powder X-ray diffractometer, scanning electron microscope, high resolution transmission electron microscope (HRTEM) and photoluminescence (PL) spectrometer. The results indicate that the phase, morphology, and size of the products can be tuned by altering reaction temperature and time. A possible formation mechanism of the microspheres was proposed based on the time-dependent experiments and HRTEM results, which contained an oriented attachment and Ostwald ripening process. Under ultraviolet excitation, the NaLa(MoO₄)₂:Eu³⁺ microcrystals exhibit strong red luminescence at 613 nm which attributes to ⁵D₀ → ⁷F₂ transition of Eu³⁺. The dependence of NaLa(MoO₄)₂:Eu³⁺ PL intensity on different morphologies have been investigated in detail. The results revealed that the PL intensity of NaLa(MoO₄)₂:Eu³⁺ microspheres is higher than that of polyhedrons and dendrites particles, and proved that the microspheres might have potential application in solid lighting technology.     

Nonionic surfactant-assisted hydrothermal synthesis of YVO4:Eu3+ powders in a wide pH range and their luminescent properties

YVO₄:Eu³⁺ powders with different morphologies were fabricated by a simple hydrothermal method at 180 °C for 24 h in a wide pH range with the assistance of polyvinylpyrrolidone (PVP) as a nonionic surfactant. The as-synthesized samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence spectroscopy (PL). The obtained results showed that the pH value of synthesis solution played a key role in the formation of final products with different morphologies, such as, microspheres, irregular microspheres with grain-like nanoparticles, stone-like structures with regular short nanorods, and smooth rhombohedrons. The PL measurements revealed that the emission intensity of the samples was first decreased, and then increased with increasing the pH value due mainly to the increase in crystallinity and decrease in surface defects.     

Preparation and luminescent properties of lanthanide (Eu3+ and Tb3+) complexes grafted to 3-aminopropyltriethoxysilane by covalent bonds

A novel precursor PMA–Si was synthesized by modifying 1,2,4,5-benzene-tetracarboxylic acid (PMA) with 3-aminopropyltriethoxysilane (APTES). Then the hybrids were prepared by PMA–Si coordinating to lanthanide ions (Eu³⁺ and Tb³⁺) in sol–gel process. In order to improve luminescent efficiency, 1,10-Phenanthroline (Phen) was introduced to the system as the second ligand. As-prepared compounds in sol condition were coated on quartz plates to form a layer of thin film, which was different from other similar hybrids. The properties of the hybrids were characterized by FT-IR, fluorescence spectra, TG and SEM. The results showed that the obtained materials enhanced thermal stability, mechanical resistances, waterproofness as well as machining properties.