Effect of structure, particle size and relative concentration of Eu(3+) and Tb(3+) ions on the luminescence properties of Eu(3+) co-doped Y(2)O(3):Tb nanoparticles

Eu(3+) co-doped Y(2)O(3):Tb nanoparticles were prepared by the combustion method and characterized for their structural and luminescence properties as a function of annealing temperatures and relative concentration of Eu(3+) and Tb(3+) ions. For Y(2)O(3):Eu,Tb nanoparticles annealed at 600 and 1200?°C, variation in the relative intensity of excitation transitions between the (7)F(6) ground state and low spin and high spin 4f(7)5d(1) excited states of Tb(3+) is explained due to the combined effect of distortion around Y(3+)/Tb(3+) in YO(6)/TbO(6) polyhedra and the size of the nanoparticles. Increase in relative intensity of the 285?nm peak (spin-allowed transition denoted as peak B) with respect to the 310?nm peak (spin-forbidden transition denoted as peak A) with decrease of Tb(3+) concentration in the Y(2)O(3):Eu,Tb nanoparticles heated at 1200?°C is explained based on two competing effects, namely energy transfer from Tb(3+) to Eu(3+) ions and quenching among the Tb(3+) ions. Back energy transfer from Tb(3+) to Eu(3+) in these nanoparticles is found to be very poor.     

BaAl_2O_4:Eu~(2+),Dy~(3+)长余辉发光材料的燃烧合成及其发光特性

以金属硝酸盐和尿素为原料,采用燃烧法合成了发青绿光的BaAl2O4:Eu2+,Dy3+长余辉发光材料。采用XRD、SEM、荧光分光光度计等手段对其进行分析表征。研究结果表明:随着燃烧温度升高,燃烧反应加剧,副产物BaCO3的含量减少,BaAl2O4的结晶程度增加,晶粒尺寸增大。Ba-Al2O4:Eu2+,Dy3+的激发光谱和发射光谱峰值分别为310nm和500nm,均呈宽谱带特征,其发光是由Eu2+的4f65d1→4f7跃迁引起,长余辉特性主要基于Dy3+的电子陷阱作用。     

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+.     

LiyMg2-x-yP2O7:xTb3+磷酸盐基质荧光粉的制备及发光性能研究

采用高温固相法制备得到了新型磷酸镁基质荧光粉LiyMg2-x-yP2O7:xTb3+,利用红外光谱(FT-IR)和X射线衍射(XRD)等手段对产品进行了表征,研究了Tb3+、Li+掺杂量对其物相及发光强度的影响。结果表明:Tb3+的掺入对其产品物相有一定影响,Li+的掺杂对产品物相影响较小。Tb3+和Li+的最佳掺杂摩尔分数均为12%,Li+的掺入对其激发峰及发射峰位置基本没有影响,但能有效提高产品的发光强度。该荧光粉的最强激发峰位于波长371nm处,最强发射峰位于波长545nm处,为绿色发光,是良好的近紫外激发绿色发光材料。     

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.     

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.     

Eu3+对Na3Gd2(BO3)3∶Tb3+发光性能的影响及其能量传递

采用高温固相法制备了Na_3Gd_2(BO_3)_3∶Tb~(3+),Eu~(3+)荧光粉,并对样品的物相组成、微观形貌、发光性能和能量传递进行了分析。结果表明,Na_3Gd_(2-x)(BO_3)_3∶xTb~(3+)荧光粉在紫外和近紫外区域有较强的激发峰,在368nm波长激发下,发射光呈绿色,Tb~(3+)最佳掺杂量为x=0.04。随着在Na_3Gd_(1.96)(BO_3)_3∶0.04Tb~(3+)中掺入Eu~(3+),Tb~(3+)对Eu~(3+)产生了以电偶极-电偶极相互作用为主的能量传递,且传递效率随Eu~(3+)掺杂量的增加而逐渐增大。发射光谱中Tb~(3+)的发射峰强度逐渐减弱,而Eu~(3+)的发射峰强度逐渐增强,导致Na_3Gd_(1.96-y)(BO_3)_3∶0.04Tb~(3+),yEu~(3+)荧光粉发光颜色由绿色向橙色变化。     

纳米Y2O2S∶Tb X射线发光粉的合成及发光性质

以EDTA为螯合剂、尿素为沉淀剂,采用络合沉淀法制备了Y2O2S:Tb纳米X射线发光粉.通过X射线衍射(XRD)、光致发光(PL)光谱和X射线激发发光(XEL)光谱对纳米发光粉进行了表征,并研究了纳米晶的发光性能及Tb3+离子的能量传递过程.研究表明:所制备样品显示了单一的六角结构,其一次粒径约为32nm.在254nm紫外光和X射线激发下,Y2O2S:Tb X射线发光粉都显示了Tb3+离子的特征发射峰,分别起源于5D3和5D4能级到基态能级的跃迁.     

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.     

Preparation and luminescence properties of LaMgAl11O19:Eu3+ phosphor powder

LaMgAl11O19, is a kind of rare earth aluminate with the hexagonal structure, which has been used as a host material for the luminescence of various rare earth and magnet-like ions. LaMgAl11O19:Eu3+ phosphors have been prepared through the one-pot method. X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA) and photoluminescence spectra were used to characterize the resulting phosphors. The results of XRD indicated that the phosphors crystallized completely at 1,400 degrees C. In LaMgAl11O19:Eu3+ phosphors, the Eu3+ shows its characteristic red emission at 615 nm (5D0-7F2) upon excitation into 404 nm, with an optimum doping concentration of 15 mol% of La3+ in the host lattices.     

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.     

Characterization and luminescence of Eu3+ ions doped 12CaO 7Al2O3 nanopowders

Eu3+ ions doped 12CaO 7Al2O3 (C12A7) powders with different Eu3+ concentrations were prepared by sol-gel combined with solid state reaction method. The results of XRD and Raman spectra showed that single cubic phase polycrystalline C12A7:Eu3+ powders were prepared. The absorption peaks attributed to f-f transition of Eu3+ ion can be observed, indicating that Eu3+ had been incorporated into C12A7 lattice site. Visible PL peaks around 578, 588, 614 nm were ascribed to 5D0 --> 7FJ (J = 0, 1, 2) transitions of Eu3+ under the excitation of 488 nm line. The PL of C12A7:Eu3+ showed the strongest emission intensity at Eu3+ concentration of 0.5 at%. Two different types of Eu3+ centers were identified by the two lines from 5D0 --> 7F0 transition emission. The doping mechanism of C12A7:Eu3+ might be attributed to Eu3+ ions substitution for two types of Ca2+ lattice sites in C12A7. The temperature dependent PL spectra of Eu-doped C12A7 were measured in the range from 100 to 300 K under the excitation of 488 nm laser line. The PL intensities as a function of temperature were well fitted by using a unified theoretical model, considering thermal activation and nonradiative energy transfer processes.     

Study on UV excitation properties of Y2O3:Ln3+ (Ln = Eu3+ or Tb3+) luminescent nanomaterials

Y2O3:Ln3+ (Ln = Eu or Tb) nanocrystals with different Ln3+ doping concentrations and average sizes were prepared by chemical self-combustion. The corresponding bulk materials with various doping concentrations were obtained by annealing the nanomaterials at high temperature. The emission spectra, excitation spectra, and X-ray diffraction spectra were used in this study. It was found that the charge transfer band of Y2O3:Eu3+ red-shifted as particle size decreased, and the charge transfer band in the 5-nm particles obviously broadened toward the long wavelength. It was also found that the profile of excitation spectra corresponding to the 4f5d (4f8 --> 4f(7)5d1) transition changed a lot with the variation of the particle size. The dependence of the excitation spectra of Y2O3:Ln3+ on particle size was investigated.     

The effects of Mn2+ doping on the luminescence properties of 12CaO 7Al2O:Eu2+ nanocrystal phosphor

The long lasting blue phosphorescence (LLP) and photostimulated luminescence (PSL) after ultraviolet light irradiation at room temperature in 12CaO 7Al2O3:xEu2+, yMn2+ (x = 0, 0.001; y = 0, 0.01) prepared by the chemical co-precipitation method were observed. It was shown that novel oxide 12CaO 7Al2O3:Eu2+, Mn2+ (C12A7:Eu2+, Mn2+) with unique nanocage structure can store energy when irradiated with 365 nm photons. And photon energy can be subsequently released by exposed to 980 nm light. The codopant Mn2+ enhances the intensity of the persistent phosphorescence and PSL due to the existence of more shallow and new deeper electron traps in C12A7: Eu2+, Mn2+. A model for energy storing and recovering and the detailed mechanism of PSL are presented through comparing with the luminescence properties of the co-doped C12A7:Eu2+, Mn2+ and C12A7:Eu2+.     

Temperature-Dependent Luminescence Characteristic of SrSi2O2N2：Eu2＋ Phosphor and Its Thermal Quenching Behavior

The yellow SrSi2O2N2：Eu2＋ phosphor has been synthesized by using a simple solid-state reaction method with Sr2SiO4：Eu2＋ as the precursor. It shows a broad excitation band extending from 250 to 520 nm and an asymmetric emission band with a main peak at about 550 nm. The emission intensity of the SrSi202N2：Eu2＋ is about 1.2 times higher than the commercial yellow phosphor YAG：Ce3＋ （P46-Y3）. The temperature- dependent luminescence characteristic of SrSi202N2：Eu2＋ has been investigated in this paper. With increasing temperature, the emission band of SrSi202N2：Eu2＋ shows anomalous blue-shift along with decreasing emission intensity and the broadening full width at half maximum （FWHM）. Particularly, compared with YAG：Ce3＋ （P46-Y3）, the yellow SrSi202N2：Eu2＋ phosphors exhibit higher thermal stability due to their weaker electron-phonon coupling strength （1.1）, lower stokes shift （0.0576 eV） and larger activation energy （0.288 eV）. All these results indicate that SrSi202N2：Eu2＋ yellow phosphors have potential application for white light-emitting diodes （LEDs）, What＇s more, an energy level scheme is constructed to explain the anomalous blue-shift phenomenon.     

Visible upconversion emission of Pr3+ doped gadolinium gallium garnet nanocrystals

The luminescence properties of a Pr3+-doped gadolinium gallium garnet (GGG, Gd3Ga5O12) nanocrystalline host were investigated. Dominant blue/green emission was observed emanating from the 3P0 --> 3H4 transition after excitation using a wavelength of 457.9 nm. Continuous wave excitation into the 1D2 level of the Pr3+ ion at 606.9 nm transition produced blue upconversion luminescence spectra, ascribed to emission from the 3P1 --> 3H4 and 3P0 --> 3H4 transitions. The increase in the decay times of the observed transitions following excitation with 606.9 nm is indicative of the dominance of an energy transfer upconversion (ETU) mechanism relative to excited state absorption (ESA). Furthermore, blue, green and red upconversion emission was observed from the 3P0, 3P1 and 1D2 states following excitation into the 1G4 energy level with 980 nm. No change in the decay times of the emitting states was observed following excitation with a wavelength of 980 or 457.9 nm; hence, upconversion was determined to primarily occur through ESA. The luminescence properties of the nanocrystals are compared to a single crystal of GGG:Pr3+ (bulk) with an identical Pr3+ concentration (1%).     

Study on luminescent properties of Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors prepared by co-precipitation

Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors with different concentrations have been prepared by co-precipitation. XRD (X-ray diffraction) and SEM (scanning electron microscopy) were used to investigate the structure and morphology. The emission spectra, excitation spectra and fluorescence decay curves were measured, and partial J-O parameters and quantum efficiencies of Eu3+ 5D0 energy level were calculated. Furthermore, concentration quenching curves of Eu3+ in different hosts were drawn. The photoluminescent properties of Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors have been studied. The results indicate that Eu3+ 5D0-7F2 red luminescence can be effectively excited by 395 nm and 465 nm in Gd2WO6 and Gd2W2O9 hosts, similar to the familiar Gd2(WO4)3:Eu. Especially Gd2W2O9:Eu has strong red emission and high quenching concentration, so it has potential applications for trichromatic white LED as red fluorescent materials.     

Synthesis and luminescence properties of lanthanide (III)-doped YF3 nanoparticles

Synthesis process and luminescence properties of trivalent lanthanide ions (Ln3+) doped YF3 nanoparticles have been investigated. To synthesis Ln(3+)-doped YF3 nanoparticles, the mixture of (YCl3 x nH2O + LnCl3 x nH2O), and NH4F was hydrothermal treated at 180 degrees C in a Teflon-liner auto-clave or heated at higher temperatures (400 degrees C - 600 degrees C) in a stove. The XRD patterns showed that the Ln(3+)-doped orthorhombic YF3 nanoparticles with no second phase have been prepared. The solid solution Y(1-x)Eu(x)F3 (x = 0 - 0.4) nanoparticles have been synthesized. The luminescence concentration quenching resulted from resonance energy transfer between neighboring Eu3+ ions occurred at higher Eu3+ concentrations (30 mol%). The upconversion luminescence of Er(3+)-Yb3+ codoped YF3 nanoparticles under 980 nm excitation has also been observed. With increase of heated temperature, the size of the Er(3+)-Yb3+ codoped YF3 nanoparticles increased gradually, and upconversion luminescence intensity increased significantly.     

荧光粉Sr3-x-yAl2O6∶xCe3+,yEu2+的制备及其发光特性

采用高温固相反应法制备了Sr3-x-yAl2O6:xCe3+,yEu2+(x=0,y=0;x=0.04,y=0;x=0.04,y=0.02;x=0.04,y=0.04;x=0.04,y=0.06;x=0.04,y=0.08;x=0,y=0.04)荧光粉,研究其相组成与荧光特性,结果表明,样品具有单相Sr3Al2O6晶体结构。在360nm波长的紫外光激发下,Ce3+离子辐射出峰值在434nm附近的宽谱蓝光。通过能量传递作用,Eu2+离子辐射峰值为517nm左右的宽谱绿光。Ce3+和Eu2+的荧光组合获得了色坐标为(0.2611,0.3313)的近白光发射。样品的激发光谱分布在250～400nm的波长范围,这种荧光粉有望在紫外或近紫外激发的白光LED中获得应用。     

Structure, charge transfer bands and photoluminescence of nanocrystals tetragonal and monoclinic ZrO2:Eu

Eu(3+)-doped tetragonal and monoclinic ZrO2 (called t-ZrO2:Eu and m-ZrO2:Eu, respectively) nanoparticles were prepared using the Pechini sol-gel process. The samples were characterized via X-ray diffraction (XRD) and field-emission-scanning electron microscopy (FE-SEM), and with photoluminescence spectra. The influences of the Eu3+ concentration and the fired temperature on the crystal phase composition of the tetragonal and monoclinic ZrO2:Eu were reported. The typical interesting photoluminescence (PL) properties of the t-ZrO2:Eu and m-ZrO2:Eu nanoparticles were presented. In the t-ZrO2:Eu and m-ZrO2:Eu, the main emission peaks were at 607 and 615 nm, respectively, both of which originated from the 5D0-7F2 transition. The excitation band of the t-ZrO2:Eu powder with a lower Eu3+ doping concentration that was obtained at a low temperature (450 degrees C) consisted of a broad band of 230-500 nm. Both broad excitation bands in the t-ZrO2:Eu and m-ZrO2:Eu were ascribed to the O(2-) - Eu3+ charge transfer (CT) transition. The reason was discussed based on the relationship between the CT energy and its crystal structure. The CT energy of m-ZrO2:Eu is higher than that of t-ZrO2:Eu. A detailed chemical bond analysis was performed to explore the CT energy difference between t-ZrO2: Eu and m-ZrO2:Eu.