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+.     

Luminescent properties of rare earth ions in one-dimensional oxide nanowires

Rare-earth doped one-dimensional oxide nanowires including LaPO4, La2O3, and Gd2O3 were synthesized by the hydrothermal method. Their luminescent properties including local environments, electronic transitions, energy transfer, and frequency up-conversion luminescence processes were systematically studied. In LaPO4:Eu and La2O3:Eu nanowires, different symmetry sites of Eu3+ ions were identified, which obviously differed from those of the corresponding micrometer-sized particles. This was attributed to crystal field degeneration in the fringe along the length axis. In LaPO4:Eu nanowires, the electronic transition rate of 5D1-sigmaJ7FJ increased approximately 2 times over that of the zero-dimensional nanoparticles and micrometer-sized particles, which was related to the variation of dipole field induced by shape anisotropy. Considering the nonradiative relaxations, meanwhile, the luminescent quantum efficiency for 5D1-sigmaJ7FJ transitions of Eu3+ in nanowires increased 100% over that in nanoparticles and 20% over that in micrometer particles. In Gd2O3:Eu3+, LaPO4:Ce3+, and LaPO4:Tb3+ nanowires and micrometer-sized particles, the electronic transition rate of rare earths had only a little variation. In LaPO4:Ce3+/Tb3+ nanowires, the energy transfer rate of Ce3+--> Tb3+ decreased 3 times compared to that in micrometer rods. Despite this, the brightness for the 5D4-7F5 green emissions of Tb3+ increased several times due to decreased energy transfer from the excited states higher than 5D4 to some defect levels. In Gd2O3:Er3+/Yb3+ nanocrystals, as the shape varied from nanopapers to nanowires, the relative intensity of up-conversion luminescence of 2H(11/2)/4S(3/2)-4I(15/2) and 4F(9/2)-4I(15/2) to the infrared down-conversion luminescence of 4I(13/2)-4I(15/2) increased remarkably, indicating efficient up-conversion luminescence. Our present results indicate that rare-earth-doped oxide nanowires is a type of new and efficient phosphors.     

Luminescence and energy transfer characteristics of Ce3+- and Tb3+-codoped nanoporous 12CaO 7Al2O3 phosphors

The novel green-emitting phosphors of 12CaO 7Al2O3:Ce3+ , Tb3+ (C12A7:Ce3+, Tb3+) were synthesized by a solid-state reaction. Upon the excitation of Ce3+ at 350 nm, the C12A7:Ce3+, Tb3+ phosphor shows intense green emissions located at 543 nm assigning to 5D4-7F5 transitions of Tb3+ ions, and weak blue emissions centered at 434 nm due to the transitions of Ce3+ 5d-4f. The photoluminescence (PL) intensity of Ce3+ decrease with increasing Tb3+ concentration, indicating the effective energy transfer (ET) occurred from Ce3+ to Tb3+ in C12A7:Ce3+, Tb3+. The ET efficiency between Ce3+ and Tb3+ in the optimum composition reaches to 99%. Based on Dexter's ET theory, we have demonstrated that the efficient ET is a resonant type via dipole-dipole mechanism with an energy transfer critical distance of 4.02 A. Our results suggested that C12A7:Ce3+, Tb3+ phosphor would be a promising green-emitting phosphor for UV-converting white light-emitting diodes.     

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.     

Investigations of Ce3+ co-doped SbPO4:Tb3+ nano-ribbons and nanoparticles by vibrational and photoluminescence spectroscopy

Nano-ribbons and very small nanoparticles (size 2-5 nm) of SbPO4 doped with lanthanide ions (Ce3+ and Tb3+) are prepared at a relatively low temperature of 120 degrees C based on a solution method. Detailed vibrational and luminescence studies on these samples establish that these lanthanide ions are incorporated at Sb3+ site of the SbPO4 lattice. The excitation spectrum corresponding to the Tb3+ emission and the excited state lifetime of the 5D4 level of Tb3+ ions in the sample confirm the energy transfer from Ce3+ to Tb3+ ions in the SbPO4 host. The extent of energy transfer from Ce3+ to Tb3+ in these samples is found to be around 60%. Dispersion of these nanomaterials in silica matrix effectively shields the lanthanide ions at the surface of the nano-ribbons/nanoparticles from the stabilizing ligands resulting in the reduction in the vibronic quenching of the excited state. Our results show significant reduction in the surface contribution in the decay curve corresponding to the 5D4 level of the Tb3+ ions after incorporating the nano-ribbons/nanoparticles in silica. These nanomaterials incorporated in silica matrix can have potential applications in bio-assays and bio-imaging.     

硬脂酸修饰LaPO4和Ce/LaPO4纳米微粒的制备及其摩擦学性能

采用共沉淀表面修饰法,制备了硬脂酸修饰LaPO4和Ce/LaPO4纳米微粒,用红外光谱仪、X射线衍射和透射电子显微镜对表面修饰纳米微粒的结构、形貌进行了表征,考察了表面修饰纳米微粒在溶剂中的分散性,利用四球试验机考察了表面修饰纳米微粒的摩擦学性能,并用扫描电镜对钢球磨斑表面形貌进行了分析.结果表明,硬脂酸修饰LaPO4...     

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。     

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.     

Upconversion luminescence enhancement in Yb3+/Tm3+-codoped Lu2O3 nanocrystals induced by doping with Li+ ions

Lutetium oxide (Lu2O3) nanocrystals doped with 2%Yb3+, 0.5%Tm3+, and various doping concentrations of Li+ (0, 3, 5, 7, 10, 12, and 15 mol%) were prepared by the sol-gel method. The dependence on different doping concentrations of Li+ ions of the structure, morphology, and the upconversion emission intensity of the Lu2O3:2%Yb3+, 0.5%Tm3+ nanocrystals was investigated. The obtained Lu2O3 nanocrystals were systematically characterized by X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), Fourier transformed infrared (FT-IR) spectra, Raman spectra, and upconversion spectra measurements. It was found that all the nanocrystals can be readily indexed to pure cubic phase of Lu2O3, indicating good crystallinity. The experimental results show that Li+ doping in Lu2O3:2%Yb3+, 0.5%Tm3+ nanocrystals can greatly enhance the upconversion emission intensity. The strong blue (490 nm) and the weak red (653 nm) emissions from the prepared nanocrystals were observed under 980 nm laser excitation, and attributed to the 1G4 --> 3H6 and 1G4 --> 3F4 transitions of Tm3+ ions, respectively. An simple analysis based on steady-state rate equations and a power-dependent study both indicate that the 1G4 levels can be populated by three-step energy transfer (ET) processes. The enhancement of the upconversion luminescence was suggested to be the consequence of the modification of the local field symmetry around the Tm3+ ion, reduced number of OH- groups, and the enlarged nanocrystal size induced by the Li+ ions.     

Eu2+、Dy3+、Li+共掺杂CaSi2O2N2荧光粉的发光性能

采用高温固相反应法制备了一系列白光LED用CaSi2O2N2:0.05Eu2+,xDy3+,xLi+(0≤x≤0.03)荧光粉.利用X射线衍射仪对样品的物相结构进行了分析,结果表明:Dy3+和Li+离子的掺入没有改变CaSi2O2N2:Eu2+荧光粉的主晶相.利用荧光光谱仪对样品的发光性能进行了测试,发现所有样品的激发光谱均覆盖了从近紫外到蓝光的较宽范围,400 nm激发下得到的发射光谱为宽波段的单峰,峰值位于545 nm左右,是Eu2+离子5d-4f电子跃迁引起的.Dy3+离子掺杂可以提高CaSi2O2N2:Eu2+荧光粉的发光强度,Dy3+与Li+共掺杂可进一步提高荧光粉的发光强度,当Dy3+和Li+的掺杂量为1mol%时,荧光粉的发光强度达到最大值,是单掺杂Eu2+的荧光粉发光强度的157%.     

新型黄绿色发光材料Sr2MgSi3O9:Ce3+,Tb3+的合成及光谱分析

采用凝胶-燃烧法在活性炭弱还原气氛下成功合成了新型荧光粉Sr2MgSi3O9 :Tb3+、Sr2MgSi3O9:Ce3+,Tb3+,用X射线粉末衍射仪(XRD)、扫描电镜(SEM)、荧光分光光度计等对合成产物进行了分析和表征.结果表明,所合成的发光材料与Sr2MgSi2O7具有相似的晶体结构,同属四方晶系.样品一次颗粒近似球形,粒径在100nm左右.Sr2MgSi3O9:Tb3+的激发光谱为一位于249nm的宽带,发射光谱主要由473、491、547、585nm等一系列发射峰组成,其中473nm(5D3→<7F3)为主发射峰,547nm(5D4→7F5)为次发射峰;样品Sr1.955MgSi3O9:Tb3+0.04,Ce3+0.005的激发光谱由峰值分别位于249和335nm的双激发带组成,其中后者为主激发带.在335nm激发下,其发射光谱由两部分组成,其中400nm附近的带状发射对应于Ce3+的发射,而491、547、588nm处的发射峰归属为Tb3+的5+D4→7FJ(J=6,5,4)跃迁发射,最强峰位于547nm,对应Tb3+的5D4→7F5跃迁.此外,探讨了Ce3+掺杂量对样品发光亮度的影响,发现Ce3+可以把能量传递给Tb3+,对Tb3+起到敏化作用.     

A study on the magnetic and photoluminescence properties of Eu(n+) and Sm3+ doped Fe3O4 nanoparticles

In this paper, Eu(n+), Sm3+ doped Fe3O4 nanoparticles were prepared via solvothermal method, in which Ferric chloride is used as the iron source, and anhydrous EuCl3, SmCl3 as doping source. Eu, Sm valence in doped Fe3O4 nanoparticles, and effects of Eu, Sm doping amount on their structure, morphology, magnetic properties and PL properties were discussed. The results show, the Eu ions had doped Fe3O4 nanoparticles in the mixed-valence state, when the Eu and Sm doping amount were increased, the doped Fe3O4 nanoparticles changed from hollow nanospheres into spherical particles, and finally changed into uniform cube-shaped particles with 13 nm in diameter. Moreover, the doping sites for doping ions in doped Fe3O4 nanoparticles were discussed from Rietveld analysis of XRD pattern of the doped Fe3O4 nanoparticles. And the changes of the magnetic and PL properties with the doping amount were further discussed. It was found that higher Sm(3+)-doping amount led to stronger magnetic dipole transitions, while the Eu(n+)-doping amount had little effect on the magnetic dipole transitions, thus resulting in different changes in their saturation magnetization with doping amount.     

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．     

Synthesis and photoluminescence of Y2O3:RE3+ (RE=Eu, Tb, Dy) porous nanotubes templated by carbon nanotubes

Y2O3:RE3+(RE=Eu, Tb, Dy) porous nanotubes were first synthesized using carbon nanotubes as template. The morphology of the coated precursors and porous Y2O3:Eu3+ nanotubes was determined by scanning electron Microscopy (SEM) and transmission electron microscopy (TEM). It was found that the coating of precursors on carbon nanotubes (CNTs) is continuous and the thickness is about 15 nm, after calcinated, the Y2O3:Eu3+ nanotubes are porous with the diameter size in the range of 50-80 nm and the length in micrometer scale. X-ray diffraction (XRD) patterns confirmed that the samples are cubic phase Y2O3 and the photoluminescence studies showed that the porous rare earth ions doped nanotubes possess characteristic emission of Eu3+, Tb3+, and Dy3+. This method may also provide a novel approach to produce other inorganic porous nanotubes used in catalyst and sensors.     

Ba2+共掺杂YPO4∶Tb3+荧光材料的水热合成与荧光性能

采用水热法合成Ba~(2+)共掺杂YPO4∶Tb~(3+)荧光材料,并通过X射线衍射(XRD)、扫描电子显微镜(SEM)和荧光分光光度计等研究了合成样品的物相组成和荧光性能,并分析了Ba~(2+)掺杂量和反应体系pH值等对合成样品的物相结构及荧光性能的影响。结果表明,反应体系pH值和Ba~(2+)掺杂量直接影响所制备样品的结构与性能。少量Ba~(2+)(≤10%,原子分数,下同)共掺杂YPO4∶1%Tb~(3+)样品均为纯相四方晶系磷钇矿结构晶体,过量Ba~(2+)掺杂导致Ba_3(PO_4)_2杂质相的出现;pH值为6的水热环境下可获得高结晶度的单一相Ba~(2+)、Tb~(3+)共掺杂YPO4样品。激发和发射光谱测试结果表明,所制备的YPO4∶1%Tb~(3+),x%Ba~(2+)样品可被225nm的紫外光有效地激发而发射出强烈的Tb~(3+)特征的黄绿色光。一定量的Ba~(2+)共掺杂可以有效地提高YPO4∶1%Tb~(3+)样品的荧光性能,但过量(高于10%)的Ba~(2+)掺杂又会导致Tb~(3+)的荧光猝灭现象出现,最佳的Ba~(2+)共掺杂量为10%。所制备的YPO4∶1%Tb~(3+),10%Ba~(2+)样品在225nm紫外光激发下位于545nm处的发射带强度是YPO4∶1%Tb~(3+)样品的1.8倍。     

ATP/CaF_2∶Ln~(3+)(Ln∶Eu,Tb,Ce/Tb)纳米粒子的制备及其荧光性能

采用两步法制备了三磷酸腺苷二钠(ATP)修饰的ATP/CaF_2∶Ln~(3+)(Ln∶Eu,Tb,Ce/Tb)纳米粒子。采用红外光谱(IR)、X-射线衍射分析(XRD)、透射电子显微镜(TEM)对所合成的纳米粒子进行结构表征,并通过荧光光谱(FS)研究了纳米粒子的荧光性能。结构研究结果表明,ATP成功地包覆在纳米粒子的表面,纳米粒子的晶相为CaF_2的立方结构,ATP/CaF_2∶Eu~(3+)、ATP/CaF_2∶Tb~(3+)、ATP/CaF_2∶Ce~(3+)/Tb~(3+)纳米粒子的平均粒径分别约为14nm、15nm、11nm。荧光性能研究表明,ATP/CaF_2∶Eu~(3+)、ATP/CaF_2∶Tb~(3+)纳米粒子基本不发射稀土离子的特征荧光,而发射出修饰剂ATP的荧光,由于Ce~(3+)对Tb~(3+)的敏化作用,ATP/CaF_2∶Ce~(3+)/Tb~(3+)纳米粒子发射出Tb~(3+)的特征荧光。     

Fabrication and up-conversion luminescence of Er3+:Y2O3 nanoparticles

Y2O3 nanoparticles doped with different concentrations of Er3+ were prepared by the co-precipitation method. X-ray diffraction and transmission electron microscopy results show that Er3+ dissolves completely in the Y2O3 cubic phase. The Er3+:Y2O3 nanoparticles are homogeneous in size and nearly spherical, and the average diameter of the particles after being calcined at 1,000 degrees C for 2 h is in the range of 40-60 nm. When Er3+:Y2O3 nanoparticles are excited under a 980 nm diode laser, there are two main emission bands: green emission centered at 562 nm corresponding to the 4S3/2/2H11/2 --> 4115/2 radiative transitions and red emission centered at 660 nm corresponding to the 4F9/2 --> 4I15/2 radiative transitions. By changing the doping concentration of Er3+ ions, the up-conversion luminescence can be gradually tuned from green to red.     

La(BO3,PO4):Ce,Tb,Gd的发光研究

以BPO4和稀土氧化物为原料制备了铈、铽、钇共掺杂的硼磷酸镧绿色荧光粉,研究了基质中Gd^3 、Ce^3 、Tb^3 的发光特性及它们之间的相互作用。在该基质中存在Ce^3 →Gd^3 、Gd^3 →Tb^3 、Ce^3 →Tb^3 的能量传递;当钆加入到铈、铽共掺杂的硼磷酸镧基质中会导致铈离子的发射减弱,铽离子^5D4→^7F1的发射显著增强,而^5D3→^7F1的发射没有明显变化,故有利于提高荧光粉的发光强度和绿色发射纯度。用硼磷酸钆作基质比用硼磷酸镧更能提高荧光粉的发光强度、发光纯度以及发光色坐标x的值,所以La(BO3,PO4):Ce,Tb,Gd和Gd(BO3,PO4):Ce,Tb均是理想的绿色发射材料。     

Tunable luminescence and energy transfer properties of Sr₃AlO₄F:RE³+ (RE = Tm/Tb, Eu, Ce) phosphors

Sr(3)AlO(4)F:RE(3+) (RE = Tm/Tb, Eu, Ce) phosphors were prepared by the conventional solid-state reaction. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL) spectra, as well as lifetimes were utilized to characterize samples. Under the excitation of UV light, Sr(3)AlO(4)F:Tm(3+), Sr(3)AlO(4)F:Tb(3+), and Sr(3)AlO(4)F:Eu(3+) exhibit the characteristic emissions of Tm(3+) ((1)D(2)→(3)F(4), blue), Tb(3+) ((5)D(4)→(7)F(5), green), and Eu(3+) ((5)D(0)→(7)F(2), red), respectively. By adjusting the doping concentration of Eu(3+) ions in Sr(3)AlO(4)F:0.10Tm(3+), 0.10Tb(3+), zEu(3+), a white emission in a single composition was obtained under the excitation of 360 nm, in which an energy transfer from Tb(3+) to Eu(3+) was observed. For Sr(3)AlO(4)F:Ce(3+),Tb(3+) samples, the energy transfer from Ce(3+) to Tb(3+) is efficient and demonstrated to be a resonant type via a dipole-quadrupole interaction by comparing the experimental data and theoretical calculation. Furthermore, the critical distance of the Ce(3+) and Tb(3+) ions has also been calculated to be 9.05 ?. The corresponding luminescence and energy transfer mechanisms have been proposed in detail. These phosphors might be promising for use in near-UV LEDs.     

Fluorescence dynamics and rate equation analysis in Er3+ and Yb3+ doped double tungstates

The fluorescence dynamics in Er3+ and Yb3+ doped KGd(WO4)2 and KY(WO4)2 has been investigated. Lifetimes have been measured for the Yb (2F(5/2)), Er (4I(13/2)), and Er (4S(3/2)) levels around 1, 1.5, and 0.55 microm, respectively. The Yb (2F(5/2)) lifetimes show a decreasing trend toward the limiting Er (4I(11/2)) lifetime with increasing Er-to-Yb concentration ratio, whereas the Er (4I(13/2)) lifetimes are mostly unaffected by the doping concentrations. A rate equation analysis has been performed to explain the observed behavior and gain is calculated for a continuous-wave laser at 1.53 microm to find the optimum doping concentrations for high gain.