Nanostructured CaWO4, CaWO4:Eu3+ and CaWO4:Tb3+ particles: sonochemical synthesis and luminescent properties

Nanostructured CaWO4, CaWO4:Eu3+, and CaWO4:Tb3+ phosphor particles were synthesized via a facile sonochemical route. X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence, low voltage cathodoluminescence spectra, and photoluminescence lifetimes were used to characterize the as-obtained samples. The X-ray diffraction results indicate that the samples are well crystallized with the scheelite structure of CaWO4. The transmission electron microscopy and field emission scanning electron microscopy images illustrate that the powders consist of spherical particles with sizes from 120 to 160 nm, which are the aggregates of even smaller nanoparticles ranging from 10 to 20 nm. Under UV light or electron beam excitation, the CaWO4 powder exhibited a blue emission band with a maximum at 430 nm originating from the WO4/2- groups, while the CaWO4:Eu3+ powder showed red emission dominated by 613 nm ascribed to the 5D0 --> 7F2 of Eu3+, and the CaWO4:Tb3+ powders showed emission at 544 nm, ascribed to the 5D4 --> 7F5 transition of Tb3+. The PL excitation and emission spectra suggest that the energy is transferred from WO4/2- to Eu3+ CaWO4:Eu3+ and to Tb3+ in CaWO4:Tb3+. Moreover, the energy transfer from WO4/2- to Tb3+ in CaWO4:Tb3+ is more efficient than that from WO4/2- to EU3+ in CaWO4:Eu3+. This novel and efficient pathway could open new opportunities for further investigating the novel properties of tungstate materials.     

Dy3+掺杂CaWO4荧光粉体的制备及发光性能

采用固相陶瓷方法制备了Dy3+掺杂的CaWO4∶Dyx3+荧光粉体。采用XRD、SEM和FT-IR对制备粉体的微观结构进行了表征;采用荧光分析法研究了制备的荧光体的室温光致发光性能;探讨了掺杂剂Dy3+浓度对CaWO4∶Dyx3+荧光粉体的微结构和光致发光性能的影响。结果表明,制备的CaWO4∶Dyx3+荧光粉体为白钨矿结构,Dy3+的掺入会抑制CaWO4∶Dy3x+晶粒的生长。当Dy3+的掺入量为1%(摩尔分数)时,其在480nm(蓝)和575nm(黄)的发射强度达到最大;随着Dy3+浓度的增加,其特征发射峰(480nm和575nm)强度反而逐渐下降。     

Spherical SiO2 @ GdPO4: Eu3+ core-shell phosphors: sol-gel synthesis and characterization

Nanocrystalline GdPO4 : Eu3+ phosphor layers were coated on non-aggregated, monodisperse and spherical SiO2 particles by Pechini sol-gel method, resulting in the formation of core-shell structured SiO2 @ GdPO4 : Eu3+ particles. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL), low-voltage cathodoluminescence (CL), time-resolved PL spectra and lifetimes were used to characterize the core-shell structured materials. Both XRD and FT-IR results indicate that GdPO4 layers have been successfully coated on the SiO2 particles, which can be further verified by the images of FESEM and TEM. Under UV light excitation, the SiO2 @ GdPO4 : Eu3+ phosphors show orange-red luminescence with Eu3+ 5D0-7F1 (593 nm) as the most prominent group. The PL excitation and emission spectra suggest that an energy transfer occurs from Gd3+ to Eu3+ in SiO2 @ GdPO4 : Eu3+ phosphors. The obtained core-shell phosphors have potential applications in FED and PDP devices.     

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.     

Polyol-mediated synthesis and photoluminescent properties of Ce3+ and/or Tb3+-doped LaPO4 nanoparticles

Rare-earth ion (Ce3+, Tb3+) doped LaPO4 nanoparticles were prepared by the polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), UV-vis absorption spectroscopy, photoluminescence (PL) spectroscopy, and lifetimes. The results of XRD indicate that the as-prepared nanoparticles are well-crystallized at 160 degrees C and assigned to the monoclinic monazite structure of the LaPO4 phase. The obtained LaPO4:Ce3+, Tb3+ nanoparticles are spherical with narrow size distribution and average size of 20 nm. The doped rare-earth ions show their characteristic emission in LaPO4 nanoparticles, i.e., Ce3+ 5d-4f and Tb3+ 5D4-7FJ (J = 6-3) transitions, respectively. The optimum doping concentration for Tb3+ in La(0.8-x)Ce0.2TbxPO4 nanoparticles is determined to be 15 mol% (x = 0.15). The luminescence decay curves of Ce3+ in LaPO4:Ce3+ and LaPO4:Ce3+, Tb3+ nanoparticles present a single-exponential behavior, and the lifetimes (tau) of Ce3+ decrease with increasing Tb3+ concentrations (at the constant Ce3+ concentration) in LaPO4:Ce3+, Tb3+ nanoparticles due to the energy transfer from Ce3+ to Tb3+. The energy-transfer efficiency from Ce3+ to Tb3+ was calculated, which depends on the doping concentrations of Tb3+ if the concentration of Ce3+ is fixed.     

Luminescence characteristics of Pr3+ ion doped CaTiO3 nanopowder phosphors synthesized by solvothermal method

In display applications, each displays technique needs different phosphors according to its applications. So, in this paper, nano-sized red emitting CaTiO3:Pr3+ powder phosphors were prepared by solvothermal reaction method. The phase purity and the structure of the phosphors were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM). The particles show the spherical morphology, which indicates the good luminescent characteristics. The luminescent properties of CaTiO3:Pr3+ powder phosphors have been carried out by the measurement of their phototluminescence (PL) and phototluminescence excitation (PLE) spectra. The PL spectra shows the strong red emission due to 1D2 --> 3H4 transition. The emissions of intra-4f transitions from the excited states (1D2) to the ground state (3H4) of Pr3+ are mainly observed around from 612 to 618 nm. The effect of the Pr3+ concentration on their photoluminescent properties was investigated extensively. These luminescent powders are expected to find potential applications such as optical display systems.     

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.     

Environmentally friendly aqueous solution synthesis of hierarchical CaWO4 microspheres at room temperature

An environmentally friendly route for the synthesis of hierarchical CaWO4 microspheres with novel morphology at room temperature has been successfully developed. CaCl2 and Na2WO4 were used as reaction regents, and distilled water was used as an environmentally friendly solvent. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence spectroscopy. This green wet-chemical route provides a simple, one-step, low-cost approach for the large-scale synthesis of hierarchical CaWO4 microspheres with relatively uniform diameters of 3-6 microm. The hierarchical microspheres are built up with numerous nanorods with an average diameter of 50 nm, which are radially oriented to the microsphere center. SEM observations of different intermediates indicate the possible growth process, in which the hierarchical structure growth is from nuclei through kayak-like, rod-like, peanut-like, dumbbell-like, and peach-like structures to final microspheres, via "self-assembled preferential end growth" of kayak-like particles in aqueous solution. The hierarchical CaWO4 microspheres exhibit a strong, broad blue emission peak of 412 nm.     

Sol-gel fabrication and photoluminescence properties of SiO2 @ Gd2O3:Eu3+ core-shell particles

A uniform nanolayer of europium-doped Gd2O3 was coated on the surface of preformed submicron silica spheres by a Pechini sol-gel process. The resulted SiO2 @ Gd2O3:Eu3+ core-shell structured phosphors were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as kinetic decays. The XRD results show that the Gd2O3:Eu3+ layers start to crystallize on the SiO2 spheres after annealing at 400 degrees C and the crystallinity increases with raising the annealing temperature. The core-shell phosphors possess perfect spherical shape with narrow size distribution (average size: 640 nm) and non-agglomeration. The thickness of the Gd2O3:Eu3+ shells on the SiO2 cores can be adjusted by changing the deposition cycles (70 nm for three deposition cycles). Under short UV excitation, the obtained SiO2@Gd2O3:Eu3+ particles show a strong red emission with 5D0-7F2 (610 nm) of Eu3+ as the most prominent group. The PL intensity of Eu3+ increases with increasing the annealing temperature and the number of coating cycles.     

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.     

Synthesis and luminescence properties behavior of Eu(3+)-doped nanocrystalline and bulk GdVO4 phosphors by high-energy ball milling and solid state reaction

Europium-doped nanosized-GdVO4:Eu3+ powders and bulk GdVO4:Eu3+ powders were synthesized using a planetary ball mill and conventional solid state reaction method, respectively. The effects of the grain size on the crystallinity, morphology, structure and luminescence spectra were investigated by X-ray diffraction, field emission-scanning electron microscopy and photoluminescence spectroscopy (PL). The room temperature PL spectra of the GdVO4:Eu3+ nanophosphors showed four emission bands at 611, 615, 619 and 595 nm. The bands at 611, 615 and 619 nm were assigned to the 5D0 --> 7F2 transition of the EU3+ ion when excited with 312 nm light.     

Synthesis and characterization of indium hydroxide truncated polyhedral microcrystals

Indium Hydroxide Truncated Polyhedral Microcrystals (IHTPM) have been synthesized by hydrothermally treating commercial indium oxide powders in the sodium hydroxide solution without the aid of any surfactants. The formation mechanism of the IHTPM has been proposed by adjusting the reaction time, which indicates the excessive NaOH in the system plays an important role in the formation process of the IHTPM. X-ray powder diffraction (XRD), field scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and photoluminescence (PL) spectra have been used to characterize the products. The emission spectrum shows that the IHTPM display an emission wave band from about 415 to 550 nm and exhibit two emission peaks locating at 419.2 nm and 496.6 nm, respectively.     

Photoluminescence properties of MgAl2O4:Dy powder phosphor

Trivalent dysprosium (Dy³⁺) activated magnesium alluminate phosphors were synthesized by high temperature solid state reaction method. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting phosphors. The results show that the obtained MgAl₂O₄:Dy³⁺ phosphors have good crystallinity, spherical morphology with sizes ranged from 120 to 140 nm and strong blue emission under an excitation of 258 nm. The emission spectrum of this phosphor consists of two emission bands: blue band and yellow band, and the emission intensity of the former is stronger than that of the later. Luminescence quenching is explained and the corresponding luminescence mechanisms have been proposed.     

CaWO_4粉体和CaWO_4一维阵列的制备及光致发光特性

采用溶胶-凝胶法及辅助氧化铝模板法分别制备CaWO4粉体和CaWO4一维阵列,研究合成CaWO4粉体和一维陈列的光致发光特性。结果表明,制备的样品是纯CaWO4粉体;CaWO4粉体的强发光峰是位于410 nm的宽带谱,而CaWO4一维阵列的强发光峰在450 nm处,其光致发光曲线呈现宽化和强发光峰位的红移,这是样品和模板的光致发光光谱耦合的结果。     

Fabrication of novel luminor Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+) with core/shell heteronanostructure

A novel polychromic phosphor with core-shell heteronanostructure has been prepared to improve the chromatic index of phosphors. As for the first example, Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+), its synthetic route, structure and optical properties are presented in this paper. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), energy-dispersive x-ray spectra (EDS) and photoluminescence (PL) were all employed to characterize the composite core-shell phosphors. The XRD, FE-SEM and HR-TEM results indicate that the SiO(2) and YVO(4):Eu(3+) layers have been successfully coated on Y(2)O(3):Eu(3+) nanoparticles and SiO(2) layer, respectively: these layers were further verified by the EDS. The PL showed that the red-emitting phosphor Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+) possessed the independent luminescent properties of both the core Y(2)O(3):Eu(3+) and the shell YVO(4):Eu(3+). The emissions were dominated by [Formula: see text] or [Formula: see text] transitions of Eu(3+) when excited with different wavelengths. Since this broad-band response to excitation in the range of 225-340?nm gave more red/dark red emissions found at 612, 616 and 620?nm, the novel phosphor Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+) could have potential biological labeling applications with wide flexibility.     

Hydrothermally-induced morphological transformation of GdVO4:Eu

The aim of the present study is to investigate the effect of a wide pH range on morphology and luminescence properties of europium-doped gadolinium vanadate (GdVO₄:Eu³⁺). GdVO₄:Eu³⁺ powders were hydrothermally synthesized at 180 °C for 24 h in a wide pH range. The as-synthesized powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectroscopy. The XRD results showed that GdVO₄:Eu³⁺ with the tetragonal structure formed at pH < 13 as a single phase and Gd(OH)₃ formed at pH ≥ 13 as a secondary phase. The SEM and TEM observations demonstrated the hydrothermally-induced morphological transformation of GdVO₄:Eu³⁺ powders by altering the pH of the synthesis solution. The possible mechanism for the morphological transformation was proposed. The intensities of the prominent peaks at 618 nm in the PL emission spectra of GdVO₄:Eu³⁺ powders considerably shift according to the specific morphology. The luminescence intensity of the octahedron- and rod-like GdVO₄:Eu³⁺ powders hydrothermally obtained at pH = 3 was the strongest one due to high packing density and high crystallinity as well as the extended reduction of the concentration of inherent defect states or adsorbed species.     

Hydrothermal synthesis and luminescence of MWO4:Tb3+ (M = Ca,Sr, Ba) microsphere phosphors

Spherical MWO₄:Tb³⁺ (M = Ca, Sr, Ba) particles were synthesized by a hydrothermal route at 180 °C for 10 h. The synthesized MWO₄:Tb³⁺ particles were characterized by X-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and luminescence spectroscopy. The XRD and FT-IR results show that MWO₄:Tb³⁺ particles with a scheelite-type crystal structure were synthesized successfully. The SEM and TEM results show that uniform spherical particles in the range of hundreds of nanometers were obtained. The possible growth mechanism may be attributed to a typical Ostwald ripening process. The excitation spectra of MWO₄:Tb³⁺ phosphors show a strong absorption band of the WO₄ ^2? group and some weak absorption bands of Tb³⁺ ions. The emission spectra of MWO₄:Tb³⁺ phosphors show the characteristic emission bands of Tb³⁺ ions. CaWO₄:Tb³⁺ sample has the highest excitation and emission intensity.     

Study on luminescent properties of Eu3+ doped new type yttrium tungsten oxide nanophosphors

In this paper, a novel nanophosphor, Y10W2O21:Eu, was synthesized through co-precipitation which is a simple and low-costing method. The structure and morphology of the nanocrystal samples were characterized by using XRD and FE-SEM. The emission spectra, excitation spectra and fluorescence decay curves were measured. J-O parameters, quantum efficiencies of Eu3+ 5D0 energy level, color coordinates and Huang-Rhys factor of Y10W2O21:Eu nanophosphors were calculated. The results indicate that EU3+ 5D0-7F2 red luminescence at 610 nm can be effectively excited by 394 nm near-UV light and 464 nm blue light in Y10W2O21 host, which is similar to the familiar Eu3+ doped tungstate phosphors (e.g., Gd2(WO4)3:Eu, CaWO4:Eu). Besides, compared with the other types of tungstate phosphors, a less expensive tungsten was used, which can effectively reduce cost. Therefore, the Y10W2O21:Eu red nanophosphors may have a potential application for white LED.     

Luminescence properties of nano-crystalline Ba3MgSi2O8:Eu2+, Mn2+ phosphors

Ba3MgSi2O8:Eu2+, Mn2+ phosphors were synthesized by the sol-gel method and high temperature solid-state reaction method, respectively. XRD (X-ray diffraction), FT-IR (Fourier transform infrared spectroscopy), PL (photoluminescence spectra), and PLE (photoluminescence excitation spectra) were measured to characterize the samples. Emission and excitation spectra of our Ba3MgSi2O8:Eu2+, Mn2+ phosphors monitored at 441, 515, and 614 nm are depicted in the paper. The emission intensities of 441 and 515 nm emission bands increase with increasing Eu2+ concentration, while the peak intensity of the 614 nm band increases with increasing Mn2+ concentration. We conclude that the 515 nm emission band is attributed to the 4f(6)5d transition of Eu2+ ions substituted by Ba2+ sites in Ba2SiO4. The 441 nm emission band originates from Eu2+ ions, while the 614 nm emission band originates from Mn2+ ions of Ba3MgSi2O8:Eu2+, Mn2+. Nano-crystalline Ba3MgSi2O8:Eu2+, Mn2+ phosphors prepared by the sol-gel method show higher color rendering and better color temperature in comparison with the samples prepared by high temperature solid-state reaction method.     

Optical properties and luminescence dynamics of Eu3+-doped terbium orthophosphate nanophosphors

The development of luminescent inorganic nanocrystals (NCs) doped with rare-earth (RE) ions has attracted increasing interest owing to their distinct optical properties and versatile applications in time-resolved bioassays, multiplex biodetection, DNA hybridization and bioimaging. Hexagonal TbPO4:Eu3+ NCs (10-30 nm) were synthesized via a facile hydrothermal method assisted with oleic acid (OA) surfactants, which exhibit tunable emissions from green to red by varying the concentration of Eu3+. The Tb3+-to-Eu3+ energy transfer efficiency observed reaches up to 94%. Different from their bulk counterparts, a new interface-state band (316 nm) in addition to the commonly observed spin-forbidden 4f-5d transition band (265 nm) of Tb3+ was found to be dominant in the excitation spectrum of NCs due presumably to the formation of surface TbPO4/OA complexes, which provides an additional excitation antenna in practical utilization. Two kinds of luminescence sites of Eu3+ in TbPO4 NCs, with the site symmetry of C2 or C1, were identified based on the emission spectra at 10 K and room temperature. Furthermore, the photoluminescence (PL) dynamics of Tb3+ ions in pure TbPO4 NCs have been revealed. Compared to the exponential PL decay in bulk counterparts induced by very fast energy migration, the non-exponential decay from 5D4 of Tb3+ in TbPO4 NCs is mainly attributed to the diffusion-limited energy migration due to more rapid energy transfer from Tb3+ to defects than the energy migration among Tb3+.