Synthesis and characterization of nanoporous NaYF4:Yb3+, Tm3+@SiO2 nanocomposites

Novel upconversion nanocomposites with nanoporous structure were presented in this paper. Silica-coated cubic NaYF₄:Yb³⁺, Tm³⁺ nanoparticles were first prepared. After annealing, monodisperse cubic/hexagonal mixed phases NaYF₄:Yb³⁺, Tm³⁺@SiO₂ nanoparticles were obtained, and the NaYF₄:Yb³⁺, Tm³⁺ cores became nanoporous. To the best of our knowledge, the nanoporous structure in NaYF₄:Yb³⁺, Tm³⁺@SiO₂ nanocomposites was observed for the first time. They demonstrate increased upconversion emission compared with unannealed dense NaYF₄:Yb³⁺, Tm³⁺ nanoparticles due to the appearance of the hexagonal NaYF₄:Yb³⁺, Tm³⁺. The silica shell not only makes the nanocomposites possess bio-affinity but also protects the NaYF₄:Yb³⁺, Tm³⁺ cores from aggregating and growing up. Thus the upconversion, nanoporous and bio-affinity properties were combined into one single nanoparticle. The nanocomposites have been characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD) and emission spectroscopy. These multifunctional nanocomposites are expected to find applications in biological fields, such as biolabels, drug storage and delivery.     

Synthesis and optical properties of BaTiO3:Eu3+@SiO2 glass ceramic nano particles

BaTiO₃:(5 %)Eu³⁺ nanoparticles and BaTiO₃:(5 %)Eu³⁺@SiO₂ composites were synthesized by the solvothermal method. The effects on the structure, morphology and luminescent properties were studied using samples with different molar ratios of BaTiO₃:(5 %)Eu³⁺@SiO₂: 60:40, 50:50, 40:60, 30:70, 20:80, 10:90, 08:92, 6.5:93.5, 05:95, and 1.5:98.5. When the amount of silica in the composites was increased, the orange emission of Eu³⁺ increased, too; this was observed by exciting the charge transfer band centered at 283 nm. Furthermore, an increase in the intensity of the emission was obtained under excitation at 394 nm as a consequence of the improvement in the crystallinity of the samples. The presence of silica and the degree of crystallinity of the samples were determined through the Fourier transform infrared spectra and X-ray diffraction patterns. All of the results suggest that our ceramic material could be a good candidate for biomedical applications such as biolabeling, since the luminescence of BaTiO₃:(5 %)Eu³⁺@SiO₂ composites have an emission intensity higher than that of nanoparticles composed solely of BaTiO₃:Eu³⁺. This work demonstrates that BaTiO₃:Eu³⁺@SiO₂ composites have an emission intensity higher than that of nanoparticles composed solely of BaTiO₃:Eu³⁺.     

Optical-transition Probability of Tm^3＋ Ions in Tm^3＋／Er^3＋：YVO4 Crystal

1INTRODUCTIONThelasersoperatedataround2mmwavelengthhavegainedmuchinterestbecauseofvariousappli-cations,e.g.(1)groundorspaceremotesensingforLIDARandmetrology,(2)medicalapplicationssinceliquidwaterhasastrongabsorptionbandnear2mm,and(3)eyesafelaser[1,2].The2…     

Fe_3O_4/Au composite nano-particles and their optical properties

The colloid gold and magnetic particle modified with various chemical groups have been widely used in the areas of biomedical and molecular biology[1―6]. Therefore, a great deal of attention has been given to the preparation and application of colloid go…     

Upconversion properties of Er3+, Yb3+ and Tm3+ codoped fluorophosphate glasses

Er3+, Yb3+ and Tm3+ codoped fluorophosphate glasses emitting blue, green and red upconversion luminescence at 970 nm laser diode excitation were studied. It was shown that Tm3+ behaves as the sensitizer to Er3+ for the green upconversion luminescence through the energy transfer process: Tm3+:3H4+Er3+:4I 15/2-->Er3+:4I 9/2+Tm3+:3H6, and for the red upconversion luminescence through the energy transfer process: Tm3+:3F4+Er3+:4I 11/2-->Tm3+:3H6+Er3+:4F 9/2. Moreover, Er3+ acts as quenching center for the blue upconversion luminescence of Tm3+. The sensitization of Tm3+ to Er3+ depends on the concentration of Yb3+. The intensity of blue, green and red emissions can be changed by adjusting the concentrations of the three kinds of rare earth ions. This research may provide useful information for the development of high color and spatial resolution devices and white light simulation.     

Synthesis of colloidal upconverting NaYF4 nanocrystals doped with Er3+, Yb3+ and Tm3+, Yb3+ via thermal decomposition of lanthanide trifluoroacetate precursors

Upconverting lanthanide-doped nanocrystals were synthesized via the thermal decomposition of trifluoroacetate precursors in a mixture of oleic acid and octadecene. This method provides highly luminescent nanoparticles through a simple one-pot technique with only one preparatory step. The Er3+, Yb3+ and Tm3+, Yb3+ doped cubic NaYF4 nanocrystals are colloidally stable in nonpolar organic solvents and exhibit green/red and blue upconversion luminescence, respectively, under 977 nm laser excitation with low power densities.     

Investigations of the optical spectra and EPR parameters in CaWO4:Yb3+

In this paper, we calculate the optical spectra data (crystal-field energy levels), the electron paramagnetic resonance (EPR) g factors gparallel, gperpendicular of Yb3+ and hyperfine structure constants Aparallel, Aperpendicular of 171Yb3+ and 173Yb3+ isotopes in CaWO4 crystal in a unified way from the crystal-field theory. All the calculated results are in good agreement with the experimental values. The signs of Aparallel and Aperpendicular for both isotopes 171Yb3+ and 173Yb3+ are suggested.     

Rattle-type hollow CaWO4:Tb(3+)@SiO2 nanocapsules as carriers for drug delivery

Rattle-type hollow nanocapsules are among of the most promising candidates as drug carriers owing to their huge inner space and multifunctional material combination. In this paper, rattle-type hollow CaWO(4):Tb(3+)@SiO(2) nanocapsules with a diameter of 100-110 nm and a wall thickness around 10 nm were fabricated. The hollow silica nanospheres were used as nano-reactors and the luminescent core of CaWO(4):Tb(3+) was post-filled into the nano-reactors by a vacuum nano-casting route combined with a Pechini-type sol-gel method. Subsequently, doxorubicin hydrochloride (DOX), a model of an anti-cancer drug, is loaded into the CaWO(4):Tb(3+)@SiO(2) nanocapsules and their cell cytotoxicity, cancer cell uptake and drug release behavior are investigated in vitro. The prepared multifunctional inorganic nanocapsules show a loading capacity for DOX as high as 124 mg g(-1) and sustained-release properties. The release profile of the drug from DOX-loaded nanocapsules can last over five days. Besides, the blank CaWO(4):Tb(3+)@SiO(2) shows very low cytotoxicity against cancer cell lines (HeLa cell) while the DOX-loaded nanocapsules exhibit relatively high efficiency for killing of HeLa cells. The rapid cancer cell uptake process is observed by confocal laser scanning microscopy. The results indicate that a rattle-type hollow CaWO(4):Tb(3+)@SiO(2) nanocapsule has the potential to be used as drug carrier in therapy. Moreover, it is possible to extend the synthetic strategy in this study to other rattle-type multifunctional composites to meet various demands.     

Synthesis and Infrared Multi‐band Absorption Properties of Core‐shell NaYF4:Yb3+, Er3+@SiO2 Nanoparticles

Due to the unique size effects, nanomaterials in infrared absorption have attracted much attention for their strong absorption in the infrared region. To achieve the infrared multi‐band absorption, we propose to synthesize a core‐shell structure nanomaterial consisting of NaYF₄:Yb³⁺, Er³⁺ core and a layer of SiO₂ as shell. A series of NaYF₄:Yb³⁺, Er³⁺ nanocrystals were synthesized through hydrothermal method by adjusting the ratio of citric acid(CA)‐to‐NaOH, and the effects of CA concentration, and NaOH concentration were studied in detail. NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanoparticles were synthesized by sol‐gel method using TEOS as silica source. The results show that the core‐shell NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanoparticles were successfully synthesized. Up‐conversion spectra of these nanoparticles were recorded with 980 nm laser excitation under room temperature. There are no changes of the emission centers of nanoparticles before or after silica coating, but the emission intensities of nanoparticles after silica coating are weakened. Furthermore, the property of infrared multi‐band absorption was tested through ultraviolet‐visible‐near infrared spectrophotometer and infrared absorption spectra. The results illustrate that the multi‐band infrared absorption nanomaterial was successfully synthesized.     

Thermal and optical properties of Tm3+ doped tellurite glasses

Ultraviolet, visible (UV/VIS) and differential thermal analysis (DTA) measurements were carried out in order to investigate the optical and thermal properties of various 0.5 mol.% Tm2O3 containing (1 - x)TeO2 + xLiCl glasses in molar ratio. The samples were prepared by fusing the mixture of their respective reagent grade powders in a platinum cricuble at 750 degrees C for 30 min. DTA curves taken in the 23-600 degrees C temperature range with a heating rate of 10 degrees C/min reveal a change in the value of the glass transition temperature, Tg, while melting was not observed for the glasses containing LiCl content less than 50 mol.%. These glasses were found to be moisture-resistant. However, the glasses with LiCl content higher than 50 mol.%, in which a melting peak was observed at Tc = 401 degrees C, were moisture-sensitive. Absorption measurements in the UV/VIS region of the glasses without Tm2O3 content show that the Urbach cutoff occurs at about 320 nm and, is relatively independent of the LiCl content. Six absorption bands were observed in the Tm2O3 doped glasses corresponding to the absorption of the 1G4, 3F2, 3F3 and 3F4, 3H5 and 3H4 levels from the 3H6 ground level of Tm3+ ions. The spectra also show that the integrated absorption cross-section of each band depends on the glass composition. Judd-Ofelt theory was used to determine the Judd-Ofelt parameters as well as the radiative transition probabilities for the metastable levels of Tm3+ ions in (0.3)LiCl + (0.7) TeO2: 0.01 Tm2O3 glass which is moisture-resistant.     

Controllable synthesis and luminescent properties of three-dimensional nanostructured CaWO4:Tb3+ microspheres

Three-dimensional (3D) nanostructured CaWO(4):Tb(3+)microspheres assembled by submicrospindles were synthesized via a mild sonochemical route from an aqueous solution of CaCl(2), TbCl(3) and Na(2)WO(4) with the aid of surfactant Polyglycol 600 (PEG-600). The crystal structure and morphology of the as-prepared products were characterized by using X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). Rietveld refinement was carried out on the XRD data. The results showed that the CaWO(4):Tb(3+)nanoparticles can be formed without ultrasonic irradiation or addition of PEG-600. With continuously increasing irradiation time the submicrospindles and microspheres could be self-assembled. The central diameter and length of the submicrospindles are around 190 and 500 nm, respectively. The 3D CaWO(4):Tb(3+)nanostructured microspheres with diameter of 2-4 μm were assembled by the submicrospindles. A possible formation mechanism for the 3D-structured CaWO(4):Tb(3+)microspheres was proposed. The Photoluminescent (PL) properties of Tb(3+) ions in the nanostructured CaWO(4) microspheres were studied. The energy transfer processes in CaWO(4):Tb(3+)microspheres were analyzed. The electric dipole-dipole energy transfers related to (5)D(3) level were studied by inspecting the fluorescence decay of (5)D(3) level. The energy transfer critical distance was estimated.     

SrCO3:Tb3+ hollow microspheres fabricated via solvothermal process and their optical properties

Well-dispersed SrCO₃:Tb³⁺ hollow microspheres have been synthesized in the water-ethanol-ethylene glycol solvent system using oleic acid (OA) as an additive without further annealing treatment. X-ray diffraction (XRD), fourier transform-infrared spectroscopy (FT–IR), and field emission scanning electron microscopy (FE-SEM), as well as photoluminescence spectroscopy (PL) were used to characterize the resulting samples. The dosage of OA and the reaction time play key roles in the formation of the final samples. The possible formation mechanism for SrCO₃:Tb³⁺ hollow microsphere is proposed. The SrCO₃:Tb³⁺ phosphors show strong photoluminescence with green emission ⁵D₄–⁷F₅ (544 nm) as the most prominent group under ultraviolet excitation, which have potential applications in field emission displays. The present synthesis process may be extended to fabricate other inorganic materials with special morphologies and functions.     

Thermal properties and optical transition probabilities of Tm3 + doped TeO2-WO3 glass.

Glasses with the composition of (1 - x)TeO2 + (x)WO3, where x = 0.15, 0.25 and 0.3 were prepared and, their thermal and absorption measurements were carried out. Differential thermal analysis (DTA) curves taken in the 23-600 degrees C temperature range with a heating rate of 10 degrees C/min reveal a change in the value of the glass transition temperature, Tg, while crystallization was not observed for the glasses containing a WO3 content of more than 15 mol%. All the glasses were found to be moisture-resistant. The absorption bands corresponding to the absorption of the 1G4, 3F2, 3F3 and 3F4, 3H5 and 3H4 levels from the 3H6 ground level of the Tm3+ ion were observed in the optical absorption spectra. Integrated absorption cross-sections of each band except that of 3H5 level was found to vary with the glass composition. Judd-Ofelt analysis was carried out for the samples doped with 1.0 mol% Tm2O3. The omega2 parameter shows the strongest dependence on the host composition and it increases with the increasing WO3 amount. The value of omega4 increases rather slowly while the value of omega6 is practically independent of the composition. The strong dependence of the parameter omega2 indicates that this parameter is related to the structural change and the symmetry of the local environment of the Tm3+ ions in this glass.     

Microwave synthesis and photoluminescent properties of Sr2CeO4/Ln3+ (Ln = Er, Ho, Tm)

Sr₂CeO₄/Ln³⁺ (Ln = Er, Ho, Tm) phosphors were synthesized with the microwave radiation method for the first time. The luminescent properties of the samples were investigated and the up-conversion luminescence of Er³⁺, Ho³⁺ and Tm³⁺ doped Sr₂CeO₄ phosphors was observed. The spectra indicate that the energy transfer takes place from the triplet excited state of MLCT (metal-to-ligand charge transfer) state for Sr₂CeO₄ (sensitizer) to the rare earth ions (activator). __________ Translated from Journal of Hebei Normal University (Natural Science Edition), 2007, 31(2): 212–216 [译自: 河北师范大学学报 (自然科学版)]     

Synthesis and optical properties of Gd2O3:Pr3+ phosphor particles

Spherical-shaped Gd₂O₃:Pr³⁺ phosphor particles were prepared with different concentrations of Pr³⁺ using the urea homogeneous precipitation method. The resulting Gd₂O₃:Pr³⁺ phosphor particles were characterized by X-ray diffraction, field emission scanning electron microscope, and photoluminescence spectroscopy. The effects of the Pr³⁺ doping concentration on the luminescent properties of Gd₂O₃:Pr³⁺ phosphors were investigated. Photoluminescence measurements revealed the Gd₂O₃:1?% Pr³⁺ phosphor particles to have the strongest emission. The luminescence properties of Gd₂O₃:Pr³⁺ particles are strongly affected by the phosphor crystallinity and X-ray diffraction measurements confirmed that the crystallinity of Gd₂O₃ cubic structure could be enhanced by increasing the firing temperature. The luminescent Gd₂O₃:Pr³⁺ phosphor particles have potential applications in areas, such as optical display systems, lamps and etc.     

核-壳结构Pd-Co3O4@SiO2催化剂的低浓度甲烷催化燃烧性能

用自组装法制备了一种具有核–壳结构的Pd-Co₃O₄@SiO₂催化剂,对其低浓度甲烷催化燃烧性能进行了研究。TEM、XRD、H₂-TPR表征及催化活性测试结果表明,SiO₂壳内的PdO与CoO_x之间的强相互作用,使得Pd-Co₃O₄@SiO₂对低浓度甲烷燃烧具有优异的催化活性。同时,与负载型Pd/Co₃O₄-SiO₂及Pd/Co₃O₄@SiO₂催化剂相比,核-壳型Pd-Co₃O₄@SiO₂催化剂经800 ℃煅烧后仍能保持较好的核-壳结构,有效地避免了Pd和Co活性物种的高温烧结,因而具有更高的热稳定性。     

Er~(3+)∶Yb~(3+)∶Tm~(3+)共掺硼硅酸盐玻璃光致发光温度特性和能级劈裂

高温固相烧结法制备了Er^3＋：Yb^3＋：Tm^3＋共掺硼硅酸盐玻璃．在978nm半导体激光器抽运下,测量了样品在300～573K下光致发光谱强度随温度的变化,讨论了室温时上转换绿光和红光等波段的光谱劈裂．分析了Er^3＋：Yb^3＋和Tm^3＋之间的能量传递机制．研究结果表明,当温度升高时,Er^3＋：Yb^3＋：Tm^3＋共掺硼硅酸盐玻璃的481nm蓝光、517和534nm绿光、以及657nm红光等光致发光强度单调下降,在490K时几乎消失．但900nm左右的近红外光谱则随温度的升高而持续增强,而且其中心波长向短波方向移动．在室温时,光谱劈裂明显,高温时劈裂逐渐消失．     

Synthesis of Gd3PO7:Eu nanospheres via a facile combustion method and optical properties

Eu³⁺-doped Gd₃PO₇ nanospheres with an average diameter of ∼300 nm and a narrow size distribution have been prepared by a facile combustion method and structurally characterized by X-ray diffraction and field emission scanning electron microscopy. The luminescent properties were systemically studied by the measurement of excitation/emission spectra, and emission spectra under different temperatures, as well as by photostability. The strong red-emission intensity peaking at 614 nm originates the ⁵D₀→⁷F₂ transition and is observed under 254-nm irradiation, indicating that Eu³⁺ ions in Gd₃PO₇ mainly occupied non-centrosymmetry sites. The CIE1931 XY chromaticity coordinates of Gd₃PO₇:Eu³⁺ nanospheres are (x=0.654, y=0.345) in the red area, which is near the National Television Standard Committee standard chromaticity coordinates for red. Thus, Gd₃PO₇:Eu³⁺ nanospheres may be potential red-emitting phosphors for PDP and Xe-based mercury-free lamps.