Hydrothermal synthesis and photoluminescence of Eu(2-x)Sm(x)Sn2O7 (x = 0-2.0) nanophosphors

Eu(2-x)Sm(x)Sn2O7 (x = 0, 0.1, 0.5, 1.0, 1.5, and 2.0) solid solutions were successfully synthesized by a simple, mild hydrothermal process. The crystal structure, particle size, and chemical composition of the solid solutions were characterized by X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy. X-ray diffraction patterns and transmission electron microscopy images reveal that all the products were cubic pyrochlore-type Eu(2-x)Sm(x)Sn2O7 nanocrystals with the diameter of approximately 20 nm. Due to efficient energy transfer from Sm3+ to Eu3+, the Eu(2-x)Sm(x)Sn2O7 (x = 0.1, 0.5, 1.0, and 1.5) nanocrystals exhibited strong 5D0 --> 7F1 photoluminescence emission of Eu3+. The dominant 5D0 --> 7F1 transition revealed good monochromaticity and low distortion of the Eu(2-x)Sm(x)Sn2O7 nanophosphors.     

Sensitized upconversion emissions of Tb3+ by Tm3+ in YF3 and NaYF4 nanocrystals

Yb3+-Tm3+-Tb3+-codoped YF3 and NaYF4 nanocrystals (NCs) were synthesized using a simple hydrothermal method. Under 980 nm excitation, violet and ultraviolet upconversion (UC) emissions of 5D3 --> 7FJ (J = 6, 5, 4) and 5D4 --> 7FJ (J = 6, 5, 4, 3) of Tb3+ ions were observed with the fluoride NCs. In the Yb-Tm-Tb codoped NCs, energy transfer (ET) processes from Tm3+ to Tb3+ were proposed to be the main mechanisms for the UC emissions of Tb3+ ions. They are more efficient than the phonon assisted cooperative sensitization of the Yb3+ couple proposed previously for similar material system. The analysis of power dependence indicated that populating the 5D4 level of the Tb3+ ions was a four photon UC process, which demonstrated the existence of the two step ET process of Yb3+ --> Tm3+ --> Tb3+. It was also found that UC luminescence properties of Tb3+ ions were sensitive to crystal structures.     

Preparation and the luminescent properties of Tb3+-doped Gd2O3 fluorescent nanofibers via electrospinning

Tb(3+)-doped Gd(2)O(3) (Gd(2)O(3):Tb(3+)) nanofibers were prepared via a simple electrospinning technique using poly(ethylene oxide) (PEO) and rare-earth acetate tetrahydrates (Ln(CH(3)COO)(3)·4H(2)O (Ln = Gd, Tb)) as precursors. The obtained nanofibers have an average diameter of about 80 nm and are composed of pure cubic Gd(2)O(3) phase. A possible formation mechanism for the nanofibers is proposed on the basis of the experimental results, which reveals that PEO acts as the structure directing template during the whole electrospinning and subsequent calcination process. The luminescent properties of the nanofibers were investigated in detail. The nanofibers exhibit a favorable fluorescent property symbolized by the characteristic green emission (545 nm) resulting from the 5D4-->7F5 transition of Tb(3+). Concentration quenching occurs when the Tb(3+) concentration is 3 at.%, indicating that the Gd(2)O(3):Tb(3+) nanofibers have an optimum luminescent intensity under such a doping concentration.     

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.     

苯二甲酸铽与1,10-邻菲哕啉三元配合物的合成及性质

以邻(间、对)苯二甲酸[o(m、p)-PA]和1,10_邻菲啰啉(phen)为配体,合成了5种Tb(Ⅲ)的三元配合物.各配合物的组成分别为:Tb_2(m-PA)_3(phen)_2·6H_2O、Tb_2(p-PA)_3(phen)_2·2H_2O、Tb_2(o-PA)_3phen·4H_2O、Tb_2(m-PA).phen·4H_2O和Tb_2(p-PA)_3phen·4H_2O.红外光谱分析表明,在各配合物中羧基氧原子和1,10-邻菲啰啉中的氮原子均参与了配住.5种配合物均有较好的热稳定性,它们的热稳定性顺序为:Tb_2(m-PA)_3(phen)_2·6H_2O>Tb_2(p-PA)_3(phen)_2·2H_2O>Tb_2(m-PA)_3phen·4H_2O>Tb_2(o-PA)_3phen·4H_2O>Tb_2(p-PA)_3phen·4H_2O.在室温条件下,5种铽的三元固体配合物均发出绿色荧光,它们在最佳发射峰~5D_4→~7F_5(545nm)时的荧光强度顺序为:Tb_2(p-PA)_3phen·4H_2O>Tb_2(rn-PA)_3(phen)_2·6H_2O>Tb_2(p-PA)_3(phen)_2·2H_2O>Tb_2(m-PA)_3phen·4H_2O>Tb_2(o-PA)_3phen·4H_2O.     

Synthesis and characterization of novel thermoresponsive fluorescence complexes based on copolymers with rare earth ions

The thermo-sensitive and fluorescent complexes containing Eu(III) or Tb(III) were synthesized and characterized, in which cholesterol-g-poly(N-isopropylacrylamide) (PNIPAM) copolymer was used as a polymer ligand. The results from the experiments indicated that Eu(III) or Tb(III) was bonded to nitrogen and oxygen atoms in the polymer chain. The fluorescence lifetimes of the powdered Eu(III) and Tb(III) complexes was 11.48 ms and 10.71 ms, respectively. The maximum emission intensity of the PNIPAM–Eu(III) complex at 613 nm and the PNIPAM–Tb(III) complex at 545 nm were enhanced about 11.1 and 11.3 times compared with that of the corresponding rare earth ions, respectively. Additionally, the lower critical solution temperature (LCST) of complexes were slightly higher than those of the copolymers.     

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.     

Preparation and characterization of ternary europium nanorod complexes with UV excitation of the characteristic red luminescence

Rare-earth luminescent complex have been attracted increasing interest since they can emit fluorescence using near ultraviolet as excitation wavelength. Nanomaterials have potential applications in optical, electronic, magnetic fields due to their surface effects, volume effects, quantum size effects and macroscopic quantum tunnel effects. Combing the important properties of fluorescence and nanomaterial, the study of nanosized rare earth fluorescence complex is an interesting topic. In this paper, we synthesized ternary luminescence complex nanorods composed of europium (Eu (III))-trimesic acid (H3L)-1,10-phenanthroline (phen) using co-precipitation method in the polyvinylpyrrolidone (PVP) matrix. The elemental analyses of the samples were determined using an Inductively coupled plasma atomic emission spectroscopy (ICP-AES), and the chemical composition PVP/EuL(phen)0.2 5H2O was obtained. The X-ray diffraction (XRD) patterns showed that the resulting nano-sized complex is new substance different from that of two ligands. The transmission electron microscopy (TEM) image indicated that the nano-sized complex was nanorod with the average diameter of about 50 nm. Thermal analysis (TGA) result exhibited that the nano-sized complex is stable under 400 degrees C. UV-Vis diffuse reflectance spectra (DRS) showed that there is the maximum absorption at 260 nm. Photoluminescence analysis (PLA) indicated that the nano-sized complex emits Eu (III) characteristic red luminescence under ultraviolet excitation.     

Synthesis of the Fe3O4@SiO2@SiO2-Tb(PABA)3 luminomagnetic microspheres

In this paper, we describe the synthesis and characterization of a luminomagnetic microspheres with core-shell structures (denoted as Fe3O4@ SiO2 @SiO2-Tb(PABA)3). The luminomagnetic microspheres were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometer (VSM), and photoluminescence spectrophotometer (PL). The SEM observation shows that the microsphere consists of the magnetic core with about 400 nm in average diameter and silica shell doped with terbium complex with an average thickness of about 90 nm. It has a saturation magnetization of 15.8 emu/g and a negligible coercivity at room temperature and exhibits strong green emission peak from 5D4 --> 7F5 transition of Tb3+ ions. The luminomagnetic microspheres with good magnetic response and fluorescence probe property as well as water-dispersibility would have potential medical applications, such as time-resolved fluoroimmunoassay (TR-FIA), fluorescent imaging, and magnetic resonance imaging (MRI).     

Study on luminescence behavior of BaAl12O19:Tb, Eu

BaAl12O19:Tb, Eu phosphors were prepared by sol-gel technique. The luminescence properties and the energy transfer between Eu2+ and Tb3+ were investigated. For BaAll2O19:Tb phosphor, the strongest excitation peak and emission peak produced from Tb3+ transition of 5D4-7F5 were at 240 nm and at 550 nm respectively, while the peak shape was narrow and peak intensity was large. The Eu2+ added in the BaAl12O19:Tb induced energy transfer to Tb3+ and different color luminescence from blue (400 nm) to green (570 nm) was obtained by changing the ratio of Tb3+/Eu2+ with excitation at 240 nm.     

Dispersion of luminescent nanoparticles in different derivatives of poly(ethyl methacrylate)

Gd2O3:Tb(5%) nanoparticles were prepared via the polyol route and dispersed without any stabilizer in several ethyl methacrylate derivatives matrices such as poly(ethyl methacrylate), poly(2-methoxyethyl methacrylate) and poly(2-hydroxyethyl methacrylate) (PHEMA). Nanocomposites were obtained via free-radical polymerization of methacrylic monomers with ethylene glycol dimethacrylate as crosslinker and colloidal solution of Gd2O3:Tb(5%) nanoparticles. Best results are obtained with PHEMA in which the dispersed Gd2O3:Tb(5%) nanoparticles are spherical with a mean diameter of 15 nm, as measured by TEM. The obtained solid Gd2O3:Tb(5%)/PHEMA nanocomposites are highly transparent (in the visible spectral range) and exhibit characteristic photoluminescence of Tb3+ 5D4-7F(J) (J = 6-3), with 5D4-7F5 strong green emission at 536 nm upon UV excitation. The nanoparticles and nanocomposites have been well characterized by high-resolution transmission electron microscope (TEM), UV/Vis transmission spectra, photoluminescence excitation, and emission spectra.     

Electrospun Fe3O4/PVP//Tb(BA)3phen/PVP magnetic–photoluminescent bifunctional bistrand aligned composite nanofibers bundles

Fe₃O₄/PVP//Tb(BA)₃phen/PVP magnetic–photoluminescent bifunctional bistrand aligned composite nanofibers bundles based on Fe₃O₄ nanoparticles (NPs) and terbium complex Tb(BA)₃phen (BA = benzoic acid) were fabricated by employing a parallel axial electrospinning setup and were characterized by X-ray diffraction, field-emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), transmission electron microscopy, fluorescence spectroscopy, and vibrating sample magnetometer. It is found that Fe₃O₄ NPs were only dispersed into one strand of the bistrand aligned composite nanofibers bundles, but no nanoparticles in the other strand. And the average diameter of the individual strand fiber was 200 ± 25 nm. The bistrand aligned composite nanofibers bundles exhibit strong green emissions under the excitation of 275 nm ultraviolet light, and the ⁵ D ₄ → ⁷ F ₅ hypersensitive transition at 545 nm was the predominant emission peak of Tb³⁺ ions. The newly obtained bifunctional nanofibers bundles exhibit excellent magnetism and high fluorescence intensity and are expected to apply in biology cell separation, magnetic resonance imaging, drug deliver, and fluorescence immunoassays/imaging.     

White luminescence of Dy3+ ions doped 12CaO 7Al2O3 nanopowders under UV light excitation

12CaO 7Al2O3:Dy3+ nanopowders were successfully synthesized by the chemical co-precipitation method. X-ray diffraction result shows that the single 12CaO 7Al2O3 phase is formed with Dy3+ ions to replace the Ca2+ ions in the host of 12CaO 7Al2O3. The yellow and blue emissions, attributed to the forced electric dipole transition of 4F(9/2) --> 6H(13/2) centered at 571 nm and the magnetic dipole transition of 4F(9/2) --> 6H(15/2) centered at 480 nm, respectively, were observed. The integrated intensity ratios of yellow to blue increase from 1.63 to 1.70 with Dy3+ concentration increasing from 0.8 to 2.0% for the as-prepared 12CaO 7Al2O3:xDy3+ phosphor. The significantly enhanced emission intensities of 12CaO 7Al2O3:1.0% Dy3+ phosphor annealed at 900 degrees C for 2 hours in vacuum ambient could be ascribed to the decrease of OH(-) groups and the change of the surface topography. The thermal stability and the Commission International de l'Eclairage coordinates were also investigated. All the photoluminescence characteristics indicate that Dy3+ ions doped 12CaO 7Al2O3 may be a good candidate for the solid state lighting phosphor as well as white light-emitting diodes.     

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.     

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.     

溴氧镧铽镝的发光特性及能量传递机理

使用高温常压方法合成了稀土发光材料ＬａＯＢｒ２Ｄｙ＾３＋，Ｔｂ＾３＋，研究了其结构，紫外４主阴极射线激发下的激发与发射光谱，Ｄｙ＾３＋的掺杂可将Ｔｂ＾３＋的＾５Ｄ３能级激光能有地弛豫到＾５Ｄ４能级，从而使５Ｄ４－Ｆ（Ｊ＝０，１）的发射，尤其是＾５Ｄ４－＾７Ｆ５的发射增强，发光亮度提高。     

Enhanced ultraviolet upconversion luminescence of Tm and Yb codoped ZrF4-BaF2-LaF3-AlF3-NaF glass

Ultraviolet (UV) upconversion (UC) luminescence properties of Tm3+ ions sensitized by Yb3+ ions in ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) glass were studied in detail. Under the excitation from a 980 nm continuous wave (CW) diode laser, red, blue, and even UV emissions were observed in the fluorozirconate glass. Several fluorescence bands appeared in the UC emission spectrum from 292.8 nm to 805.8 nm. The UC emission peaks at 291 nm, 347 nm, 363 nm, 454 nm, 475 nm, 647 nm, 687 nm, and 804 nm correspond to the transitions of 1I6 --> 3H6, 1I6 --> 3F4, 1D2 --> 3H6, 1D2 --> 3F4, 1G4 --> 3H6, 1G4 --> 3F4, 3F3 --> 3H6, and 3H4 --> 3H6, respectively. Experimental results of intensity dependence of the up-converted fluorescence on the pump power indicate a five-photon excitation scheme of 1I6 energy level.     

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.     

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.     

Sol–gel preparation and luminescence of silica/polymer hybrid material incorporated with terbium complex

Methyl methacrylate (MMA) and ethyl methacrylate (EMA) doped with luminescent ternary europium complex (Tb(acac)₃·phen) with acetylacetone (Hacac) and 1,10-phenanthroline (phen) is incorporated into microporous silica gel, and the polymerization of MMA (and EMA), hybrid material containing Tb(acac)₃·phen has been obtained. The material exhibits good toughness and transparency. The TG-DTA curves have been determined, indicating that the hybrid matrix exhibits more thermal stability than that of the pure complex and pure polymer matrix. The luminescence spectra of all hybrid material doped with Tb(acac)₃·phen show the characteristic excitation and emission of europium ions and there exists some slight shift of maximum wavelength (about 380 nm), which implies the same energy transfer mechanism as the pure complex, and the hybrid matrix is a suitable substrate for the luminescence of europium ions. In the range of doping concentration of Tb(acac)₃·phen (0.05, 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0 wt.%), emission intensities increase with the increasing of corresponding doping concentration and concentration quenching effect has not taken place. The emission spectra of terbium complex have been intensified by incorporating it into the hybrid matrix, and the specific emission intensities per complex formula unit is increased compared with that of original complex.