Effects of co-doped Li+ ions on luminescence of CaWO4:Sm3+ nanoparticles

CaWO₄, CaWO₄:Sm³⁺ and CaWO₄:(Sm³⁺, Li⁺) nanoparticles were synthesized by the precipitation method with addition of PEG 200. The X-ray diffraction patterns show that the obtained samples have a pure tetragonal phase. The CaWO₄ sample shows an emission peak at 418 nm originating from the charge-transfer transitions within the WO₄ ^2? complex. CaWO₄:Sm³⁺ and CaWO₄:(Sm³⁺, Li⁺) samples show emission peaks originating from the f–f forbidden transitions of the 4f electrons of Sm³⁺ ions. The charge compensator of Li⁺ can enhance the emission intensity effectively. It is found that the emission intensity of CaWO₄:(3 mol% Sm³⁺, 4 mol% Li⁺) phosphor is about double that of CaWO₄:3 mol% Sm³⁺ phosphor.     

Eu3+ concentration effect on luminescence properties of YAG:Eu3+ nanoparticles

Nanocrystalline Eu³⁺-doped YAG powders were prepared by modified Pechini method. The structural properties were investigated with XRD, SEM and Raman spectroscopy. XRD pattern indicated that the phase-pure YAG:Eu³⁺ crystallites were obtained without the formation of any other phases. Raman spectrum revealed good homogeneity and crystallinity of synthesized nanopowders. The luminescent properties were studied by measurement of excitation and emission spectra, quantum yields and decay curves. The effect of Eu³⁺ concentration on ⁵D₀ level lifetime was studied. The processes resulting in the relaxation of excited state (⁵D₀ level) were discussed and the probabilities of radiative and nonradiative processes were calculated using the model of f–f transition intensities. It was found that the observed shortening of ⁵D₀ level lifetime with Eu concentration is caused by increase of nonradiative process probability.     

Synthesis and characterization of Eu3+, Ti4+ @ ZnO organosols and nanocrystalline c-ZnTiO3 thin films aiming at high transparency and luminescence

Abstract

By exploiting colloidal properties, such as transparency, rheology and versatile chemistry, we propose to synthesize new photonic nanomaterials based on colloidal solutions and thin films. This contribution highlights our efforts to elaborate and to characterize nanostructures based on the ZnO–TiO₂ system. Using a recently developed sol–gel route to synthesize new Ti⁴⁺@ZnO organosols, we were able to prepare, at relatively low temperature (400 °C) and short annealing time (15 min), highly transparent, luminescent, nanocrystalline Eu³⁺ doped c-ZnTiO₃ thin films. The organosols and thin films were characterized with UV-visible-near infrared absorption, ellipsometry, photoluminescence spectroscopy, dynamic light scattering, x-ray diffraction and scanning electron microscopy.     

Synthesis and characterization of Eu3+, Ti4+ @ ZnO organosols and nanocrystalline c-ZnTiO3 thin films aiming at high transparency and luminescence

By exploiting colloidal properties, such as transparency, rheology and versatile chemistry, we propose to synthesize new photonic nanomaterials based on colloidal solutions and thin films. This contribution highlights our efforts to elaborate and to characterize nanostructures based on the ZnO–TiO₂ system. Using a recently developed sol–gel route to synthesize new Ti⁴⁺@ZnO organosols, we were able to prepare, at relatively low temperature (400 °C) and short annealing time (15 min), highly transparent, luminescent, nanocrystalline Eu³⁺ doped c-ZnTiO₃ thin films. The organosols and thin films were characterized with UV-visible-near infrared absorption, ellipsometry, photoluminescence spectroscopy, dynamic light scattering, x-ray diffraction and scanning electron microscopy.     

Strong luminescence and efficient energy transfer in Eu3+/Tb3+-codoped ZnO nanocrystals

Single crystalline Eu³⁺/Tb³⁺-codoped ZnO nanocrystals have been synthesized by using a simple co-precipitation method. Successful doping is realized so that strong green and red luminescence can be efficiently excited by ultraviolet and near ultraviolet radiation, demonstrating an efficient energy transfer from ZnO host to rare earth ions. The energy transfer from the ZnO host to Tb³⁺ in ZnO: Tb³⁺ samples and ZnO host to Eu³⁺ in the ZnO: Eu³⁺ samples under UV excitation are investigated. It is found that the red ⁵D₀ → ⁷F₂ emission of Eu³⁺ ions decreases with increasing temperature but the green ⁵D₄ → ⁷F₅ emission of Tb³⁺ ions increases with increasing temperature, implying a different energy transfer processes in the two samples. Moreover, energy transfer from Tb³⁺ ions to Eu³⁺ ions in ZnO nanocrystals is also observed by analyzing luminescence spectra and the decay curves. By adjusting the doping concentration, the Eu³⁺/Tb³⁺-codoped ZnO phosphors emit green and red luminescence with chromaticity coordinates near white light region, high color purity and high intensity, indicating that they are promising light-conversion materials and have potential in field emission display devices and liquid crystal display backlights.     

Synthesis and luminescence properties of Eu3+ and Sm3+ doped and co-doped BiPO4 powders by a hydrothermal route

BiPO₄:Eu³⁺, BiPO₄:Sm³⁺, and BiPO₄:(Eu³⁺, Sm³⁺) powders were synthesized by a hydrothermal route. The X-ray diffraction and Fourier-transform infrared spectroscopy results show that the samples are pure hexagonal phases. The excitation spectrum of BiPO₄:Eu³⁺ sample shows the characteristic absorption peaks of Eu³⁺ corresponding to the direct excitation from the ground state to the higher excited states of the europium f-electrons. The excitation spectrum of BiPO₄:Sm³⁺ sample consists of several narrow excitation lines due to the characteristic f–f transition of Sm³⁺. The emission spectrum of BiPO₄:Eu³⁺ specimen excited by 395 nm consists of lines mainly locating in the red area. The emission spectrum of BiPO₄:Sm³⁺ sample is composed of four emission bands, which are attributed to transitions from ⁴G_5/2 excited state to ⁶H_J/2 (J = 5, 7, 9, and 11) ground states of Sm³⁺. The excitation and emission spectra of BiPO₄:(Eu³⁺, Sm³⁺) samples are different from single doped BiPO₄ samples. The introduction of Sm³⁺ can broaden and enhance the excitation intensity of Eu³⁺ and improve the emission dominance of Eu³⁺ at 617 nm.     

Synthesis and luminescence properties of ZnO:Eu3+ nano crystalline via a facile solution method

Different ZnO:Eu3+ nanocrystalline were obtained from a facile solution method with two different precipitators. The comparison of photoluminescence property of two different ZnO:Eu3+ nanocrystalline was performed. The XRD patterns and the PL spectra indirectly indicate that the dopant Eu3+ ions had entered into the crystal lattices of ZnO. The study on the PL spectra of the as-prepared ZnO:Eu3+ nanocrystalline shows that with the change of dopant concentration, the ratio of relative emission intensity of electric dipole transition to magnetic dipole transition changes, which fully expresses that the presence of the inversion centers is associated with the dopant concentration of Eu3+.     

Photoluminescence of transparent glass-ceramics based on ZnO nanocrystals and co-doped with Eu3+, Yb3+ ions

Glasses of the K₂OZnOAl₂O₃SiO₂ system co-doped with Eu₂O₃ and Yb₂O₃ were prepared by the melt-quenching technique. Transparent zincite (ZnO) glass–ceramics were obtained by secondary heat-treatments at 680–860 °C. At 860 °C, traces of Eu oxyapatite appeared in addition to ZnO nanocrystals. The average crystal size obtained from the X-ray diffraction data was found to range between 14 and 35 nm. Absorption spectra of the initial glasses are composed of an absorption edge and absorption bands due to electronic transitions of Eu³⁺ ions. With heat-treatment, the absorption edge pronouncedly shifts to the visible spectral range. The luminescence properties of the glass and glass-ceramics were studied by measuring their excitation and emission spectra at 300, 78, and 4.2 K. Strong red emission of Eu³⁺ ions dominated by the ⁵D₀–⁷F₂ (612 nm) electric dipole transition was detected. Changes in the luminescence properties of the Eu³⁺-related excitation and emission bands were observed after heat-treatments at 680 °C and 860 °C. The ZnO nanocrystals showed both broad luminescence (400–850 nm) and free-exciton emission near 3.3 eV at room temperature. The upconversion luminescence spectrum of the initial glass was obtained under excitation of the 976 nm laser source.     

Photoluminescence of ZnO:Eu3+ nanoflowers

The synthesis of ZnO:Eu3+ nanoflowers by a low-temperature hydrothermal route is described. Characterization of the materials was performed by ESEM, XRD and FTIR spectra. The 355 nm excited photoluminescence spectra at 10 K do not indicate the presence of Eu2+ or the ZnO defect states which give rise to green or red broadband emission. Excitation into the ZnO conduction band at low temperature does not give emission from Eu3+. Selective excitation of the Eu3+ emission shows that EU3+ ions occupy a variety of different sites, of which one of them is similar to EU3+ in C-type Eu2O3.     

Strong luminescence enhancement of Li2CaSiO4:Eu2+ phosphors by codoping with La3+

La³⁺ ions codoped Li₂CaSiO₄:Eu²⁺ phosphors were synthesized through the solid state reaction method. Large increases in the emission could be achieved by adding La³⁺ in the host. The optimum doping concentration expressed by the x value in Li₂Ca_0.99?xSiO₄:0.01Eu²⁺, xLa³⁺ was determined to be of 0.01. X-ray diffraction patterns revealed that the samples maintained Li₂CaSiO₄ single phase after codoping Eu²⁺ and La³⁺. The excitation spectra of samples showed a broad absorption band ranging from 220 to 450 nm and the emission spectra excited at 375 nm showed the typical broad band of Eu²⁺ peaks at about 478 nm (4f⁶5d¹–4f⁷). The broad absorption band wavelength was found to be matched appropriately with the emission wavelength of commercially available blue LEDs. Fluorescent lifetime test results showed that the La³⁺ codoped could increase the excited state energy and prolong the lifetime of Eu²⁺. The optimization mechanism was studied in detail by the case of La³⁺ codoping. The temperature dependent luminescence measurements show that the thermal quenching remains small in the case of La³⁺ doping, in other word, La³⁺ codoped Li₂CaSiO₄:Eu²⁺ phosphor has a good thermal stability. These results provided a useful basis for further improving the luminescence performance of Li₂CaSiO₄:Eu²⁺ phosphors.     

EPR,optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses

Antimony phosphate glasses (SbPO) doped with 3 and 6 mol% of Cr³⁺ were studied by Electron Paramagnetic Resonance (EPR), UV–VIS optical absorption and luminescence spectroscopy. The EPR spectra of Cr³⁺-doped glasses showed two principal resonance signals with effective g values at g = 5.11 and g = 1.97. UV–VIS optical absorption spectra of SbPO:Cr³⁺ presented four characteristics bands at 457, 641, 675, and 705 nm related to the transitions from ⁴A₂(F) to ⁴T₁(F), ⁴T₂(F), ²T₁(G), and ²E(G), respectively, of Cr³⁺ ions in octahedral symmetry. Optical absorption spectra of SbPO:Cr³⁺ allowed evaluating the crystalline field Dq, Racah parameters (B and C) and Dq/B. The calculated value of Dq/B = 2.48 indicates that Cr³⁺ ions in SbPO glasses are in strong ligand field sites. The optical band gap for SbPO and SbPO:Cr³⁺ were evaluated from the UV optical absorption edges. Luminescence measurements of pure and Cr³⁺-doped glasses excited with 350 nm revealed weak emission bands from 400 to 600 nm due to the ³P₁ → ¹S₀ electronic transition from Sb³⁺ ions. Cr³⁺-doped glasses excited with 415 nm presented Cr³⁺ characteristic luminescence spectra composed by two broad bands, one band centered at 645 nm (²E → ⁴A₂) and another intense band from 700 to 850 nm (⁴T₂ → ⁴A₂).     

Influence of the Eu3+ dosage concentration on luminescence properties of YPO4:Eu3+ microspheres

In this study, YPO₄:Eu³⁺ microspheres with different Eu³⁺ dosage concentration were fabricated by a facile hydrothermal route at 200 °C for 10 h in the presence of citric acid. The YPO₄:Eu³⁺ samples were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and luminescence spectroscopy. The XRD results reveal that the YPO₄:Eu³⁺ samples presented a tetragonal structure. The TEM and SEM observations demonstrate that the YPO₄:Eu³⁺ samples with uniform sphere-like morphologies can be obtained at 200 °C for 10 h. The sizes of samples are in the range of 2–2.2 μm. The room temperature luminescence properties of YPO₄:Eu³⁺ samples were studied using an excitation wavelength of 227 nm. The emission spectrum displays the bands associated to the ⁵D₀ → ⁷F_J (J = 1, 2 and 4) electronic transitions characteristics of the Eu³⁺ cations at different positions. The influence of Eu³⁺ dosage concentration on luminescence properties of YPO₄:Eu³⁺ microspheres were studied carefully.     

Thermally stimulated luminescence and photoluminescence investigations of Eu3+ and Eu2+ doped SrBPO5

Thermally stimulated luminescence (TSL) investigations of SrBPO₅:Eu^3?+ and SrBPO₅:Eu^2?+ phosphors were carried out in the temperature range of 300–650 K. In order to characterize the phosphors, X-ray diffraction and photoluminescence (PL) techniques were used. The emission spectrum of air heated SrBPO₅:Eu^3?+ phosphor exhibited emission bands at 590, 614, 651 and 702 nm under 248 nm excitation, assigned to transitions of Eu^3?+ ion. In phosphor prepared in reducing (Ar + 8% H₂) atmosphere, a broad emission band due to Eu^2?+ ranging from 350 to 400 nm was observed with 340 nm excitation. EPR studies have confirmed the presence of Eu^2?+ ions in the samples prepared in reducing atmosphere. TSL glow curve of SrBPO₅:Eu^3?+ had shown intense peaks around 397, 510, 547 K and a weak peak around 440 K whereas in case of SrBPO₅:Eu^2?+ system, glow peaks at 414, 478 and weak peak at 516 nm were observed. The shift in TSL glow pattern can be attributed to stabilization of different oxidation states of the dopant ion in the host lattice. Apart from this, TSL trap parameters such as trap depth and frequency factor were determined. Spectral characteristics of TSL emission have shown that Eu^3?+?/Eu^2?+ ion acts as the luminescent centre in the respective phosphors.     

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.     

掺铕氧化钇发光纳米晶的拉曼光谱研究

采用凝胶燃烧法制备了8～50nm的Y2O3:Eu3+纳米晶.利用XRD确定了纳米晶的结构及晶粒大小,测定了不同晶粒大小的纳米晶Y2O3:Eu3+的拉曼光谱.通过测定不同的激发光所激发的拉曼光谱,以及比对荧光谱,指认了纳米晶Y2O3:Eu3+的Raman振动光谱,并且观察和研究了Raman光谱随晶粒尺寸的变化,发现了低维材料的一些反常拉曼效应.     

铁铕共掺杂的TiO_2空心微球的制备及光催化活性

通过溶胶-凝胶法制备铁铕共掺杂的TiO_2(Fe~(3+)-Eu~(3+)/TiO_2)空心微球,采用XRD、TEM、BET和XPS等对样品进行表征,以亚甲基蓝(MB)的光催化降解为目标反应,评价其光催化活性。结果表明:SiO_2微球表面均匀地包覆了1层TiO_2,超声有利于提高SiO_2@TiO_2复合微球间的分散性,同时也发现煅烧前对SiO_2@TiO_2复合微球进行研磨处理后所得的Fe~(3+)-Eu~(3+)/TiO_2空心微球部分塌陷,而未研磨和煅烧后研磨所得Fe~(3+)-Eu~(3+)/TiO_2空心微球完整性较好。XRD和BET分析表明,Fe~(3+)-Eu~(3+)/TiO_2空心微球为锐钛矿且具有良好的介孔结构,铁铕共掺杂在TiO_2空心微球中产生协同作用,使Fe3+-Eu3+/TiO2空心微球的粒径进一步减小,比表面积增大。当Fe~(3+)的掺杂量为1.0%、Eu~(3+)的掺杂量为0.5%时,Fe~(3+)-Eu~(3+)/TiO_2空心微球的光催化活性最高。     

Y2O3:Eu3+ core-in-multi-hollow microspheres: facile synthesis and luminescence properties

Y2O3:Eu3+ core-in-multi-hollow microspheres were synthesized via a facile hydrothermal method in the presence of glucose followed by a subsequent heat-treatment process. X-ray diffraction (XRD) pattern shows that the as-obtained hollow spheres are cubic phase of Y2O3. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images indicate that the samples are three layer hollow spheres with a diameter of 2-4 microm and the outermost wall thickness of 100 nm, the size of the inner core is about 300-400 nm, and the sub-outer wall thickness is about 100 nm. X-ray energy dispersive spectrum (EDS) shows that the samples are composed of Y, Eu and O. Photoluminescence spectra show that the hollow spheres have a strong characteristic red emission corresponding to the 5D0 - 7F2 transition of Eu3+ ions under ultraviolet excitation. This method can be used to synthesize other rare earth oxide hollow luminescent materials.     

Efficient doping and energy transfer from ZnO to Eu3+ ions in Eu(3+)-doped ZnO nanocrystals

Successful doping of Eu3+ ions into ZnO nanocrystals has been realized by using a low temperature wet chemical doping technique. The substitution of Eu3+ for Zn2+ is shown to be dominant in the Eu-doped ZnO nanocrystals by analyzing the X-ray diffraction patterns, transmission electron microscopy images, Raman and selectively excited photoluminescence spectra. Measurement of the luminescence from the samples shows that the excited ZnO transfers the excited energy efficiently to the doped Eu3+ ions, giving rise to efficient emission at red spectral region. The red emission quantum yield is measured to be 31% at room temperature. The temperature dependence of photoluminescence and the photoluminescence excitation spectra have also been investigated, showing strong energy coupling between the ZnO host and Eu3+ ions through free and bound excitons. The result indicates that Eu3+ ion-doped ZnO nanocrystals are promising light-conversion materials and have potential application in highly distinguishable emissive flat panel display and LED backlights.     

Tunable luminescence of Dy3+ single-doped and Dy3+/Tm3+ co-doped tungsten borate glasses

RE³⁺ (RE³⁺ = Tm³⁺, Dy³⁺) ion single and co-doped tungsten borate glasses for white light emitting diodes (LEDs) were prepared by melt quenching method. Emission and excitation spectra of the glasses were measured. The color of luminescence can be tuned by changing the composition of glass matrix or the concentrations of Tm³⁺ and Dy³⁺ ions. White light emission can be achieved from 0.5Dy³⁺ single-doped 15WO₃–25La₂O₃–60B₂O₃ and 0.4Tm³⁺/1.5Dy³⁺ co-doped 50WO₃–25La₂O₃–25B₂O₃ glasses. In addition, energy transfers between Tm³⁺ and Dy³⁺ were also analyzed. The Dy³⁺/Tm³⁺ co-doped tungsten borate glasses may be potential candidates for white LED application.