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.     

Controllable morphology and high photoluminescence of (Y, Gd)(V, P) O4:Eu3+ nanophosphors synthesized by two-step reactions

Multi-ion doped YVO(4):Eu(3+) nanophosphors with high photoluminescence intensity were successfully prepared by a two-step reaction process for the first time, including YVO(4):Eu(3+) seeds synthesized by hydrothermal reaction and co-doping P(5+) and Gd(3+) in a sol-gel process. X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and photoluminescence spectroscopy were adopted to detect the structure, grain size, morphology and optical properties of the nanophosphors, respectively. Owning to the template-induced effect of the seeds, the morphology and size of the nanophosphors could be controlled by adjusting the molar ratios between the seeds and doping ions. The size of these nanophosphors increased as P(5+) and Gd(3+) co-doped. However, most of the samples kept approximately spherical morphology and narrow size distribution. The composition-optimized (Y, Gd)(V, P)O(4):Eu(3+) nanophosphors with spherical morphology in the 80-100 nm range exhibit better red emission and superior color saturation under vacuum ultraviolet excitation compared with that of the commercial phosphor (Y, Gd)BO(3):Eu(3+).     

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.     

Self-assembled peanut-like Ln3+ (Ln = Tb, Sm, Eu) doped NaLa(WO4)2: phase control and its relevance to luminescence modification

Ln3+ (Ln = Tb, Sm, Eu) doped NaLa(WO4)2 peanuts were successfully self-assembled by a facile EDTA assisted hydrothermal treatment. EDTA played critical roles in the phase and morphology control, which regulated the phase transformation from monoclinic La2(WO4)3 flowers to tetrahedral NaLa(WO4)2 peanuts. La2(WO4)3:Tb3+ exhibited two broad excitation bands at 280 and 340 nm, which are related to the normal and perturb sites of WO4(2-). However, the excitation band for NaLa(WO4)2:Tb3+ shifted to near ultraviolet region and showed only one broad excitation band originating from perturb sites. Under ultraviolet excitation, La2(WO4)3:Tb3+ displayed green light and NaLa(WO4)2:Tb3+ showed blue-green light consisting of WO4(2-) self-activated blue emission and the characteristic Tb3+ emission. It can be clearly seen that the blue emission of WO4(2-) was not sufficiently quenched in NaLa(WO4)2 as that in La2(WO4)3, because the distortions of crystalline lattice for NaLa(WO4)2 may alter the energy migration processes. When doping with Sm3+ and Eu3+, NaLa(WO4)2 peanuts exhibited white color emission which may find practical applications in solid state lighting devices.     

Study on energy transfer and energy migration of Ca2Gd8(SiO4)6O2:Dy3+ phosphor films

Being a kind of rare-earth-metal silicate with oxidapatite structure, Ca2R8(SiO4)6O2 (R = Y, Gd, La) is a promising material doped with rare earth, and widely used as phosphors. In this thesis, Ca2Gd8(SiO4)6O2:Dy3+ films were prepared by the sol-gel method. X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL) spectra, and lifetimes were used to characterize the resulting films. AFM study indicated that the phosphor films consisted of 120 nm homogeneous particles. By combining the model of Burshtein for donor-donor migration and the V-F-B model for donor-acceptor energy transfer, the experimental luminescence decay curve of 6P(J) state of Gd3+ was re-simulated. It is found that concentration quenching of Gd3+ can be due to the result of the joint action of donor-donor (Gd3+-Gd3+) energy migration and donor-acceptor (Gd3+-Dy3+) energy transfer.     

Luminescent properties and characterization of one dimensional Gd(2)O(3):Eu(3+) phosphor nano-wire for field emission application

Gd(2)O(3):Eu(3+) nano-wire phosphors embedded in SBA-15 silica templates were synthesized using a combination of the sol-gel method and hydrothermal reactions followed by a sintering process at 1000?°C. The crystal structure of Gd(2)O(3):Eu(3+) was confirmed using x-ray diffraction. Observation using transmission electron microscopy shows that the nano-wire diameters were very uniform in the 7-9?nm range. In comparison with bulk Gd(2)O(3):Eu(3+) materials, we found that the photo-luminescent property of the nano-wire was different. The analysis shows that the main nano-wire emission peaks were at 585, 597, 613 and 620?nm. The CIE value (x = 0.62, y = 0.38) indicates that the nano-wire emitted a pink colour and not red as for the bulk material. The field emission experimental results agreed well with the photo-luminescent analysis results.     

Eu3+掺杂的硼酸锶系列荧光体的合成及其发光性能

采用溶胶-凝胶法和高温固相反应法合成了Eu^3 掺杂的SrB4O7、SrB2O4、Sr2B2O5、Sr3B2O6荧光体．荧光光谱测试结果表明在不同基质中Eu^3 的荧光发射是有区别的，Sr2B2O5：Eu^3 、Sr3B2O7：Eu^3 发射峰在610nm左右的红光区，SrB2O4：Eu^3 的发射峰在593nm的橙色区，而SrB4O7：Eu^3 则表现出了Eu^2 离子的特征峰，产生这种区别主要是由Eu^3 所处的配位环境不同造成的．荧光体SrB4O7：Eu^3 、SrB2O4：Eu^3 、Sr2B2O5：Eu^3 、Sr3B2O6：Eu^3 的最佳掺杂浓度为2％左右．     

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.     

Er~(3+)掺杂透明微晶玻璃光谱性质的研究

通过高温熔融法和热处理制备了含有-γBi2WO6纳米晶的Er3+掺杂透明硼铋酸盐微晶玻璃.根据X射线粉末衍射结果和Scherrer公式计算得到-γBi2WO6晶粒大小约为15 nm.由于部分Er3+离子取代Bi3+进入-γBi2WO6纳米晶相中,使得Er3+离子在1.5μm的有效发射带宽由78 nm增加到85 nm,同时Er3+离子在4I13/2能级的荧光寿命由0.67 ms增加到1.43 ms.此外,与原始玻璃相比,在Er3+掺杂硼铋酸盐微晶玻璃中观察到强烈的绿光上转换发光,其上转换发光机制可以归为双光子过程.     

Luminescence properties of cubic HfO2-Sc2O3:Eu3+ nano-powders

The cubic nano-structured HfO2-Sc2O3:Eu3+ were successfully synthesized via a combustion process. Phase evolution of the synthesized powders was determined by X-ray diffraction measurements. Pure cubic phase of HfO2-Sc2O3 solid solution was obtained after being calcined at 800 degrees C for 2 h.The particle size and morphology were analyzed by TEM. The luminescence properties were also investigated. Photoluminescence spectra of Eu3+ doped HfO2-Sc2O3 nano-powders showed red emission at 613 nm which corresponds to the 5D0-7F2 transition of Eu3+ ion.     

Structure and Luminescence Properties of Gd2(WO4)3 and Gd2(WO4)3:Tm3+,Yb3+ Nanopowders Prepared by Solid-State Sintering and the Pechini Methods

Inorganic Materials - Gd2(WO4)3 and Gd2(WO4)3:0.5% Tm3+, 10% Yb3+ nanopowders have been prepared by the Pechini method and solid-state sintering. According to X-ray diffraction results, the...     

Preparation, characterization and spectroscopy of Eu3+ in Gd2O3 nanorods

Eu3+:Gd2O3 nanorods were prepared by a hydrothermal method. X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and Fourier transform-infrared spectroscopy were used to characterize the resulting samples. Emission and excitation spectra were studied using xenon excited spectroscopic experiments at 10 K. Energy transfer from Gd3+ to Eu3+, from the band gap of the host to Eu3+, and from Eu3+ (S6) to Eu3+ (C2) was observed. The energy levels of Eu3+ at the C2 site of cubic Gd2O3 were experimentally determined according to the fluorescence spectra at 10 K, and fit well with the theoretical values. The standard deviation for the optimal fit was 12.9 cm(-1). The fluorescent lifetime of 5D0 (2.3 ms at 295 K) was unusually longer than that of the bulk counterparts (0.94 ms), indicating a small filling factor (0.55) for the nanorod volume. However the lifetime of 5D1 was much shorter than that of the bulk counterparts, 65 micros at 10 K, 37 micros at 295 K.     

微波均相沉淀法制备Ce:(Y,Gd)_3Al_5O_(12)荧光粉

以Y2O3,Gd2O3,Ce(NO3)3·6H2O,Al(NO3)3·9H2O为原料,采用微波均相沉淀法制备了Ce:(Y,Gd)3Al5O12前驱体,经1100℃煅烧得到粒径在100nm左右的近球形粉体。测试结果表明:该粉具有良好的荧光性能,呈现宽带激发和宽带发射,激发主峰在456nm,半高宽约为60nm,在460nm入射光的激发下,发射峰在566nm左右,半高宽约为125nm。由于Gd3+的掺入改变了基体的晶场结构,致使发射光谱发生了红移。     

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.     

Cathodoluminescence of rare earth implanted Ga2O3 and GeO2 nanostructures

Rare earth (RE) doped gallium oxide and germanium oxide micro- and nanostructures, mostly nanowires, have been obtained and their morphological and optical properties have been characterized. Undoped oxide micro- and nanostructures were grown by a thermal evaporation method and were subsequently doped with gadolinium or europium ions by ion implantation. No significant changes in the morphologies of the nanostructures were observed after ion implantation and thermal annealing. The luminescence emission properties have been studied with cathodoluminescence (CL) in a scanning electron microscope (SEM). Both β-Ga(2)O(3) and GeO(2) structures implanted with Eu show the characteristic red luminescence peak centered at around 610 nm, due to the (5)D(0)-(7)F(2) Eu(3+) intraionic transition. Sharpening of the luminescence peaks after thermal annealing is observed in Eu implanted β-Ga(2)O(3), which is assigned to the lattice recovery. Gd(3+) as-implanted samples do not show rare earth related luminescence. After annealing, optical activation of Gd(3+) is obtained in both matrices and a sharp ultraviolet peak centered at around 315 nm, associated with the Gd(3+) (6)P(7/2)-(8)S(7/2) intraionic transition, is observed. The influence of the Gd ion implantation and the annealing temperature on the gallium oxide broad intrinsic defect band has been analyzed.     

Filling double-walled carbon nanotubes with WO3 and W nanowires via confined chemical reactions

Carbon nanotubes filled with metals and semiconductors have been regarded as one of the most promising materials for nanodevices. Here, we demonstrate a simple and effective method to produce tungsten trioxide (WO3) and tungsten (W) nanowires with diameters of below 4 nm inside double-walled carbon nanotubes (DWCNTs). First, the precursors, i.e., phosphotungstic acid (HPW, H3PW12O40) molecules, are successfully introduced into DWCNTs. Subsequent decomposition and reduction lead to the formation of WO3 and W nanowires inside DWCNTs. The products were carefully characterized by high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. FTIR spectra provide a direct proof that the HPW molecules enter the DWCNTs as an ionic state, i.e., PW12O40(3-) and H+, instead of the molecular state. HRTEM analysis shows that the diameter of the WO3 nanowires inside DWCNTs is 1.1-2.4 nm with the average length of 16-18 nm, and that for W nanowires is 1.2-3.4 nm with the average length of 15-17 nm. Meanwhile, DWCNTs are doped by the encapsulated WO3 and W nanowires. Tangential band shift in Raman spectra revealed the charge transfer between the nanowires and carbon nanotubes.     

High pressure luminescence and Raman studies on the phase transition of Gd2O3:Eu3+ nanorods

The cubic Gd2O3:Eu3+ nanorods were synthesized by a hydrothermal method. The SEM image indicated the nanorods with diameter of 30-35 nm and length of 200-500 nm. The structural stability of Gd2O3:Eu3+ nanorods was investigated by in situ high pressure luminescence and Raman spectra up to 18.9 GPa at room temperature. The results reveals a pressure-induced phase transition from cubic to hexagonal structure at about 11.3 GPa. After releasing pressure, the part of hexagonal structure is retained and the other transfers to monoclinic phase.     

Er3+/Yb3+掺杂NaGd(WO4)2粉体的制备与发光性能

采用水热法成功制备了Er~(3+)/Yb~(3+)双掺杂的NaGd(WO_4)_2纳米粉体,研究了不同络合剂、水热温度对样品形貌和结构的影响。测量了不同Er~(3+)掺杂浓度样品的可见上转换和近红外发射光谱。结果表明:在980nm LD激发下,可观测到样品强烈的绿色上转换发光,对应Er~(3+)的~2H_(11/2)→~4I_(15/2)(530nm)和~4S_(3/2)→~4I_(15/2)(552nm)跃迁,以及较弱的红色上转换和近红外发光,分别对应Er~(3+)的~4F_(9/2)→4I15/2(656nm)和~4I_(13/2)→~4I_(15/2)(1 532nm)跃迁。且随着Er~(3+)掺杂浓度的增加,样品的上转换红绿光和1.54μm附近的近红外光均呈现出先增大后减小的趋势。样品的激发和发射光谱显示,在378nm处的激发峰最强,对应Er~(3+)的~4I_(15/2)→~4 G_(11/2)能级跃迁,最强发射峰位于552nm。根据泵浦功率与发光强度的关系可以得出,红光和绿光的发射主要为双光子吸收过程,但红光还包含了一定的单光子吸收成分。     

The sol-gel process synthesis of GdAl3(BO3)4:Eu3+ nanophosphors

GdAl3(BO3)4:Eu3+ red phosphors were prepared using citric acid as complex agent by sol-gel technique. The preparation conditions of the precursor synthesis, including crystallization temperature and crystallization time were investigated. Their structure and luminescence properties were characterized by X-ray diffraction (XRD) analysis and fluorescence spectrometry. The results showed that GdAl3(BO3)4:Eu3+ phosphor crystallized at 960 degrees C for 2 h have been synthesized by sol-gel method. The phosphor is distributed into hexagonal system and the lattice parameters are a = 9.2992 nm c = 7.2577 nm. The excitation spectrum of Gd(0.95)Al3(BO3)4:Eu(0.05)3+ samples is complex and the frequency scale is wide. It consists of a number of main excitation transitions namely 8S(7/2) --> 6IJ (270 nm) of Gd3+, and the others 7F0 --> 5L6 (400 nm), 7F0 --> 5D2 (472 nm) and 7F0 --> 5D1 (542 nm) of Eu3+. The main emission peaks are 614 nm and 619 nm, which are the characteristic emission peaks of Eu3+. These emission peaks correspond to the transition from 5D0 to 7F2 of Eu3+. The shape and the wavelength range of the emission spectrum are similar when the sample was excited by different excitation spectrum. Only the relative intensity of the emission peaks is different from each other.     

Up-conversion fluorescence of Tm3+ and Gd3+ in Yb3+/Tm3+ co-doped Gd2O3 nanocrystals

Through a co-precipitation method Gd(OH)3:20%Yb3+, 1%Tm3+ nanorods were synthesized. After sintered at 900 degrees C for 1 h in air, the as-prepared Gd(OH)3:20%Yb3+, 1%Tm3+ nanorods were converted into Gd2O3:20%Yb3+, 1% Tm3+ nanocrystals. Crystalline phases, sizes, and morphologies of the two samples were characterized by X-ray diffraction and field emission scanning electron microscope. The up-conversion (UC) fluorescence spectra of the Gd2O3:20%Yb3+, 1%Tm3+ nanocrystals were recorded by using a fluorescence spectrophotometer with a 980 nm continuous wave laser diode as excitation source. The nanocrystals not only present characteristic blue and ultraviolet (UV) UC emissions of activated Tm3+, but also show UV UC emissions of host Gd3+. The experimental study suggests that the excitation power has great effects on UC fluorescence properties and the energy transfer from Tm3+ to Gd3+ is very efficient.