Fabrication and luminescent enhancement of Eu3+-doped Y2O3@YOF core-shell nanocrystals

In this paper, a two-step synthesis method for preparing Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals is introduced. Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals were prepared by combining an autocombustion process with a low temperature solid state reaction. X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), photoluminescence (PL) and fluorescence decay were employed to characterize the prepared samples. The results of XRD, TEM and EDS indicated that the products prepared by this method were not a mixture of Y2O3:Eu3+ and YOF:Eu3+ nanocrystals, but Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals. Compared with Y2O3:Eu3+ nanocrystals, a 20% increment in luminescence intensity was observed in the Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals, thus suggesting that coating with a YOF:Eu3+-shell can efficiently block the nonradiative relaxation channels that are induced by surface defect states.     

表面效应对YAG:Eu3+纳米晶发光特性的影响研究

分别采用沉淀法和燃烧法制备了YAG:1%Eu3+纳米晶粉末,用XRD和TEM对样品进行了结构分析和形貌表征。室温光谱分析表明,其发射主峰位于590nm,来源于5 D0→7F1跃迁,另外来源于5 D0→7F4跃迁的709nm发射也较强。另外发现,燃烧法制备的样品在不同激发波长激发时,发射光谱峰形有显著变化。对沉淀法制备的纳米微粒经盐酸"浸蚀"表面修饰后,发现395nm激发时,676nm和693nm发光显著增强,而且693nm发射的激发谱中存在两个宽激发带。对表面修饰后样品的变温发光特性研究发现,随着温度的降低,676nm发射显著增强,而693nm发射显著减弱。对于上述现象通过纳米微粒的表面效应和缺陷态进行了分析和解释。     

Optical spectroscopy of Eu3+ ions in tetragonal ZrO2 nanocrystals

A facile solvothermal method was introduced to incorporate Eu3+ ions into the monodisperse tetragonal ZrO2 nanocrystals (NCs) with small size of approximately 4 nm. The optical properties for Eu3+ doped ZrO2 NCs were investigated in detail by using the photoluminescence (PL) spectroscopy at room and low temperatures. Intense red emissions from Eu3+ ions could be achieved via the host sensitization, which was found to be much more efficient than the direct excitation of lanthanide ions. Moreover, multiple sites of Eu3+ as well as the host-to-Eu3+ energy transfer were also revealed based on the PL analyses.     

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.     

Synthesis and luminescence in sol–gel auto-combustion-synthesized $$\hbox {CaSnO}_{3}{:}\hbox {Eu}^{3+}$$ phosphor

Undoped and Eu-doped \(\hbox {CaSnO}_{3}\) nanopowders were prepared by a facile sol–gel auto-combustion method calcined at \(800{^{\circ }}\hbox {C}\) for 1 h. The samples are found to be well-crystallized pure orthorhombic \(\hbox {CaSnO}_{3}\) structure. Photoluminescence (PL) measurements indicated that the undoped sample exhibits a broad blue emission at about 420–440 nm, which can be recognized from an intrinsic centre or centres in \(\hbox {CaSnO}_{3}\). Eu-doped \(\hbox {CaSnO}_{3}\) showed broad blue emission centred about 434 nm, a weak peak at 465 nm and a sharp intense yellow emission line at 592 nm. The emission situated at 592 nm was assigned to the f–f transition of \(^{5}\hbox {D}_{0}\rightarrow ^{7}\hbox {F}_{1}\) in \(\hbox {Eu}^{3+}\) ions. The afterglow emission and PL decay results in Eu-doped \(\hbox {CaSnO}_{3}\) phosphor, which revealed that there are at least two different traps in this phosphor. From the obtained results, \(\hbox {Eu}^{3+}\)-doped \(\hbox {CaSnO}_{3}\) phosphor could be proposed as a potential white luminescent optical material.     

Synthesis and luminescence properties of Sr2SiO4: Eu3+, Dy3+ phosphors by the sol-gel method

The Sr2SiO4:Eu3+, Dy3+ phosphors for white light emitting diodes (LEDs) were synthesized by the sol-gel method. The microstructure and luminescent properties of the obtained Sr2SiO4:Eu3+, Dy3+ particles were well characterized. The results demonstrate that the Sr2SiO4:Eu3+, Dy3+ particles, which have spherical morphology, emitted an intensive white light emission under excitation at 386 nm. The phosphors show three emission peaks: the blue emission at 486 nm corresponding to the 4F(9/2)-6H(15/2) transition of Dy3+, the yellow emission at 575 nm corresponding to the 4F(9/2)-6H(13/2) transition of Dy3+, and the red emission at 615 nm corresponding to the 5D0-7F2 transition of Eu3+. At the same time, the effect of Eu3+ concentration on the emission intensities of Sr2SiO4:Eu3+, Dy3+ was investigated in detail. The phosphors used for white LEDs were obtained by combining near ultraviolet (NUV) light (386 nm) with Sr2SiO4:0.04Dy3+, 0.01Eu3+ phosphors with the characteristic of Commission Internationale de l'Eclairage (CIE) chromaticity coordinate (x, y) of (0.33, 0.34), and color temperature Tc of 5,603 K. In addition, the effect of the charge compensators (Li+, Na+, and K+ ions) on the photoluminescence (PL) emission intensities were studied.     

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+.     

白光LED用钨酸盐红色荧光粉的制备及发光特性

采用高温固相法制备了NaY(WO4)2:Eu3+发光材料。分别用X射线粉末衍射(XRD)、发光光谱(PL)等手段研究了发光粉的晶体结构以及发光性能。XRD结果表明,Eu3+掺杂浓度达到25%(摩尔分数)时,仍然能够形成纯相的NaY(WO4)2:Eu3+多晶粉末。NaY(WO4)2:Eu3+的激发光谱由强度很大的宽激发带(220～300nm)和锐线谱(峰值位于393nm和465nm)组成,其中宽激发带源于O2-→W6+和O2-→Eu3+电荷转移,锐线谱属于Eu3+的4f-4f跃迁吸收,发射光谱显示随Eu3+浓度的增大,NaY(WO42):Eu3+光发射强度逐渐增大,当Eu3+浓度为20%时,发射强度达到最大,随后出现浓度猝灭。     

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.     

Fabrication of photoluminescent S doped Y2O3:Eu3+ nanobelts

We have successfully fabricated the S doped Y(OH)3 nanobelts with 15-30 microm in length and 50-300 nm in width and S doped Y(OH)3:Eu3+ nanobelts with 4-15 microm in length and 80-500 nm in width (most between 100 and 200 nm) via a similar process for preparation of Y(OH)3 nanotubes. Photoluminescent (PL) nanobelts of S doped Y2O3:Eu3+ were obtained through dehydration of the S doped Y(OH)3:Eu3+ nanobelts at 450 degrees C in N2. The PL properties of the S doped Y2O3:Eu3+ nanobelts have been studied and evidenced that we have successfully synthesized functional S doped Y2O3:Eu3+ nanobelts with interesting photoluminescence properties.     

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.     

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.     

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.     

Structure and photoluminescent properties of microstructural YBO3 : Eu3+ nanocrystals

YBO3 : Eu3+ nanocrystals (NCs) were prepared by a hydrothermal method and characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. The results demonstrate that morphology and structure of the NCs varied strongly with hydrothermal temperature. Their luminescent properties were investigated in comparison to the bulk. A large number of NO3- groups were adsorbed at the surface of hydrothermal products, which acted as luminescent killers; Two symmetry sites of Eu3+ ions in NCs, the interior and the surface sites, were identified by the site-selective excitation and time-resolved emission experiments; The intensity ratio of 5D0-7F2 to 5D0-7F, of EU3+ at the surface site increased greatly than that at the interior site; as a result, the chromaticity was improved; The total radiative transition rate of 5D0-sigmaJ7FJ for Eu3+ at the surface site was 3-5 times larger than that at the interior.     

Synthesis and morphological control of europium doped cadmium sulphide nanocrystals

Europium doped cadmium sulphide (Cd(0.98)Eu(0.2)S) nanostructures were synthesised by chemical co-precipitation method using ethylene glycol (EG) and deionized water (Eu:CdS-1), and isopropyl alcohol (IPA) and deionized water (Eu:CdS-2) as mixed solvents. It has been found that the nanostructure of the europium doped CdS can be controlled by simply varying the mixed solvent system. Powder XRD pattern reveals the formation of hexagonal (wurtzite) and cubic (zinc blende) structure for Eu:CdS-1, and Eu:CdS-2, respectively. The crystallite size of the sample prepared using IPA and deionized water was measured to be 2.64 nm which is much smaller than that of the sample prepared using EG and deionized water as mixed solvent (3.65 nm). Morphology of the materials can also be changed from flower shaped crystals to paddy like structures by varying the mixed solvents. Band gap values of Eu3+ doped CdS nanocrystals synthesized from two different solvents were estimated using UV-reflectance spectra. The size and crystallinity of the samples were confirmed by HRTEM and SAED analysis. A significant change in the PL emission of the CdS nanocrystals was observed for the europium doped CdS which is mainly due to the presence of EU3+ ions which also play a significant role in the energy transfer process. It was also observed that the shift in the emission and efficiency depends on size and shape of the synthesised nanoparticles.     

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．     

Facile synthesis and luminescence characteristics of high-quality CdS: Eu/ZnS core/shell nanocrystals with biocompatibility

In this paper, we report a facile method to synthesize high quality CdS: Eu nanocrystals (NCs) and CdS: Eu/ZnS NCs with strong photoluminescence (PL). The influence of various experimental variables including the concentration of Eu3+ ions, the reaction time and the reaction temperature were investigated systematically. In addition, the PL properties of CdS: Eu NCs exhibited pH sensitive. Under the acid condition, pH value of the CdS: Eu NCs solution played an important role in determining PL emission intensity. However, under the alkaline condition, the obtained CdS: Eu NCs exhibited a tunable PL emission wavelength (from 490 nm to 610 nm) when pH value was adjusted from pH 7 to 10. After coating with ZnS shell, the CdS: Eu/ZnS NCs showed enhanced PL intensity compare with one of the CdS: Eu NCs. The CdS: Eu NCs and CdS: Eu/ZnS NCs were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). In addition, the biocompatibility of these NCs was measured by hemolytic test, which indicated that CdS: Eu/ZnS NCs were more biocompatible than CdS: Eu NCs at the same conditions. It can be expected that CdS: Eu/ZnS NCs are promising biolabeling materials.     

Luminescent properties of La3PO7:Eu3+ nanoparticles

La3PO7:Eu3+ samples were prepared by combustion and annealing and characterized by X-ray diffraction and transmission electron microscopy. It was found that the average size of the particles is about 80 nm. The red emission from the 5D0 --> 7F2 transition of the Eu3+ ions under ultraviolet light excitation is much stronger than the orange emission from the 5D0 --> 7F1 transition. The emission spectra, charge transfer band, laser selective excitation spectra, and time-resolved spectra indicate that symmetry of the local environment of Eu3+ lacks an inversion center and Eu3+ ions occupy at least two types of sites in the La3PO7 crystal. The superior color chromaticity compared to other phosphates and borates doped with Eu3+ means La3PO7:Eu3+ may have potential as a luminescent material.     

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.     

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.