Paramagnetism and improved upconversion luminescence properties of NaYF4:Yb,Er/NaGdF4 nanocomposites synthesized by a boiling water seed-mediated route

In a route boiling water served as reaction medium, a stoichiometric amount of rare-earth compound and fluoride are put into this system to form α-NaYF₄:Yb, Er nuclei. Then prepared sample is heated at elevated temperature to improve the fluorescence intensity, and next a NaGdF₄ shell grows on the surface of NaYF₄ nuclei. NaYF₄:Yb,Er/NaGdF₄ core–shell structured upconversion nanoparticles (CSUCNPs) have been successfully synthesized by above route. The use of boiling water decreases the cubic-to-hexagonal phase transition temperature of NaYF₄:Yb,Er to 350°C and increases its upconversion (UC) luminescence intensity. A heterogeneous NaGdF₄ epitaxially growing on the surface of Ln³⁺-doped NaYF₄ not only improves UC luminescence, but also creates a paramagnetic shell, which can be used as contrast agents in magnetic resonance imaging (MRI). The solution of CSUCNPs shows bright green UC fluorescence under the excitation at 980 nm in a power density only about 50 mW·cm^–2. A broad spectrum with a dominant resonance at g of about 2 is observed by the electron paramagnetic resonance (EPR) spectrum of CSUCNPs. Above properties suggest that the obtained CSUCNPs could be potential candidates for dual-mode optical/magnetic bioapplications.     

Structural design and synthesis of new MOO3-x interlayer bi-functional nanomaterials for enhanced up-conversion luminescence properties

A novel imaging materials based on bi-functional Fe₃O₄@M_OO_3-x@YF₃:Yb/Er nanoparticles (NPs) with strong up-conversion luminescence and magnetic properties was designed and synthesized by inlaying M_OO_3-x with localized surface plasmon resonance (LSPR) and ferromagnetic property in the bi-functional Fe₃O₄@YF₃:Yb/Er NPs. The morphology, structure and properties of Fe₃O₄@M_OO_3-x@YF₃:Yb/Er NPs are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), photoluminescence (PL) spectra, UV–Vis-NIR spectrophotometer and superconducting quantum interference devices (SQUID). It was found that the experimental conditions (reaction temperature, reaction time, the mass ratio of core:shell and oxygen pressure in heat treatment) have a certain effect on the oxygen defect concentration of the M_OO_3-x interlayer. XRD also showed the crystal structure of Fe₃O₄, Fe₃O₄@M_OO_3-x and Fe₃O₄@M_OO_3-x@YF₃:Yb/Er NPs. The SEM and TEM results showed that the average grain size of the prepared NPs were 200 nm. The SQUID and PL results showed that the Fe₃O₄@M_OO_3-x@YF₃:Yb/Er NPs have stronger magnetism (14.3 emu/g) and excellent up-conversion luminescence performance (the emission peak at 525 nm is nearly 20 times higher than the corresponding emission intensity of the Fe₃O₄@YF₃:Yb/Er). The Fe₃O₄@M_OO_3-x@YF₃:Yb/Er NPs can be easily used to magnetic resonance and fluorescence dual-mode image-guided visual delivery drug and also increase the accurate diagnosis and treatment effect of malignant tumor.     

Direct imaging the upconversion nanocrystal core/shell structure at the subnanometer level: shell thickness dependence in upconverting optical properties

Lanthanide-doped upconversion nanoparticles have shown considerable promise in solid-state lasers, three-dimensional flat-panel displays, and solar cells and especially biological labeling and imaging. It has been demonstrated extensively that the epitaxial coating of upconversion (UC) core crystals with a lattice-matched shell can passivate the core and enhance the overall upconversion emission intensity of the materials. However, there are few papers that report a precise link between the shell thickness of core/shell nanoparticles and their optical properties. This is mainly because rare earth fluoride upconversion core/shell structures have only been inferred from indirect measurements to date. Herein, a reproducible method to grow a hexagonal NaGdF(4) shell on NaYF(4):Yb,Er nanocrystals with monolayer control thickness is demonstrated for the first time. On the basis of the cryo-transmission electron microscopy, rigorous electron energy loss spectroscopy, and high-angle annular dark-field investigations on the core/shell structure under a low operation temperature (96 K), direct imaging the NaYF(4):Yb,Er@NaGdF(4) nanocrystal core/shell structure at the subnanometer level was realized for the first time. Furthermore, a strong linear link between the NaGdF(4) shell thickness and the optical response of the hexagonal NaYF(4):Yb,Er@NaGdF(4) core/shell nanocrystals has been established. During the epitaxial growth of the NaGdF(4) shell layer by layer, surface defects of the nanocrystals can be gradually passivated by the homogeneous shell deposition process, which results in the obvious enhancement in overall UC emission intensity and lifetime and is more resistant to quenching by water molecules.     

Catalytic Activity of the Spinel Ferrite Nanocrystals on the Growth of Carbon Nanotubes

We prepared three ferrite nanocatalysts: (i) copper ferrite (CuFe₂O₄) (ii) ferrite where cobalt was substituted by nickel (Ni _x Co_1?x Fe₂O₄, with x=0, 0.2, 0.4, 0.6), and (iii) ferrite where nickel was substituted by zinc (Zn _y Ni_1?y Fe₂O₄ with y=1, 0.7, 0.5, 0.3), by the sol-gel method. The X-ray diffraction patterns show that the ferrite samples have been crystallized in the cubic spinel structural phase. We obtained the size of grains by field emission scanning electron microscopy images and their magnetic properties by vibrating sample magnetometer. Next, carbon nanotubes were grown on these nanocatalysts by the catalytic chemical vapor deposition method. We show that the catalytic activity of these nanocrystals on the carbon nanotube growth depend on cation distributions in the octahedral and tetrahedral sites, structural isotropy, and catalytic activity due to cations. Our study may have applications in finding a suitable candidate of doped ferrite nanocrystals as catalysts for carbon nanotube growth. More interestingly, the yield of fabrication of carbon nanotubes can be considered as an indirect tool to study catalytic activity of ferrites.     

Citric acid-assisted growth of lanthanide ions co-doped one-dimensional upconversion microcrystals and their photovoltaic applications

We report for the first time the preparation of Yb³⁺–Er³⁺ co-doped β-phase sodium gadolinium fluoride (NaGdF₄:Yb/Er) microcrystals using citric acid (CA) as a shape modifier and the application of NaGdF₄:Yb/Er to amorphous silicon solar cells. The proposed hydrothermal method was facile and eco-friendly. It was found that CA played a critical role in the shape evolution of the final products. The related synthesis mechanisms are discussed. Under 980 nm laser excitation, the optimized NaGdF₄:Yb/Er crystals exhibited strong upconversion (UC) emissions at visible wavelengths. Amorphous silicon thin film solar cells were designed and fabricated for investigating different UC configurations. In combination with a metallic back reflector, the cell with the front side UC layer achieved a six-fold improvement of the photocurrent while the cell with the rear side UC layer exhibited a ten-fold enhancement of the photocurrent, under 980 nm light, compared with the cell without upconverter.     

Up-conversion emissions characteristics of non-aqueous sol-gel derived RE3Al5O12 nanocrystals

The RE3Al5O12 (REAG:Er3Al5O12, Er:Y3Al5O12 and Er:Yb3Al5O12) up-conversion (UC) nanocrystals have been prepared by the non-aqueous sol-gel method. The green and red UC emissions are attributed to the 2H(11/2), 4S(3/2) --> 4I(15/2) and 4F(9/2) --> 4I(15/2) transitions of Er3+, respectively, were obtained for all samples with a 975 nm semiconductor LD excitation. For Er3Al5O12 nanocrystals, the green and red UC emissions have similar intensities. Y and Yb ions have no evident effect on the peak positions, but strongly affected the intensities of the green and red UC emissions of the Er. A much higher intensity of the green relative to red UC emission was observed for Er:Y3Al5O12 nanocrystals, however, the red UC emission became predominant for Er:Yb3Al5O12 nanocrystals. It was suggested that the two-photon process was responsible for the green and red UC emissions mechanism for all the samples.     

Room-temperature facile synthesis of hexagonal NaYF4 and NaYF4: Yb,Er powder without any organic additives and its upconversion fluorescence properties

Based on the structure difference between cubic and hexagonal phases, a facile method was designed for the synthesis of pure hexagonal phase β-NaYF₄ and β-NaYF₄: Yb, Er powder at room temperature and ambient pressure. In the whole process, neither any organic additives, nor high temperature and high pressure were involved that indicated an environmentally friendly technology. The optimal synthesis conditions for hexagonal phase at room temperature is the pH value between 5.0 and 6.5, the amorphous Y (OH) ₃ as Y precursor and the F^?/Y³⁺ molar ratio equal to 6:1. A possible preparation mechanism based on the difference between the coordination structure of the hexagonal and the cubic phases was also proposed. It is found that the as prepared powder of the hexagonal phase can emit red upconversion luminescence with a high R/G ratio, which is significantly different from the light emitted by the usually synthesized hexagonal phase. This method can also provide a new perspective for studying the sustainable synthesis of rare earth compounds.     

Magnetic order in the Nd,Gd, Er,and Yb trifluoromethane sulfonates

We have observed magnetic order, apparently dipolar in origin, in the hexagonal trifluoromethane sulfonate salts of Nd, Gd, Er, and Yb. With the exception of Yb, their magnetic properties are all very similar to the corresponding isostructural rare earth ethyl sulfates. The Yb salt is unique in having a different ionic ground state, and may not haveC _3h symmetry.     

Synthesis of Brightly PEGylated Luminescent Magnetic Upconversion Nanophosphors for Deep Tissue and Dual MRI Imaging

A method is developed to fabricate monodispersed biocompatible Yb/Er or Yb/Tm doped β‐NaGdF₄ upconversion phosphors using polyelectrolytes to prevent irreversible particle aggregation during conversion of the precursor, Gd₂O(CO₃)₂?H₂O:Yb/Er or Yb/Tm, to β‐NaGdF₄:Yb/Er or Yb/Tm. The polyelectrolyte on the outer surface of nanophosphors also provided an amine tag for PEGylation. This method is also employed to fabricate PEGylated magnetic upconversion phosphors with Fe₃O₄ as the core and β‐NaGdF₄ as a shell. These magnetic upconversion nanophosphors have relatively high saturation magnetization (7.0 emu g^?1) and magnetic susceptibility (1.7 × 10^?2 emu g^?1 Oe^?1), providing them with large magnetophoretic mobilities. The magnetic properties for separation and controlled release in flow, their optical properties for cell labeling, deep tissue imaging, and their T₁‐ and T₂‐weighted magnetic resonance imaging (MRI) relaxivities are studied. The magnetic upconversion phosphors display both strong magnetophoresis, dual MRI imaging (r₁ = 2.9 mM^?1 s^?1, r₂ = 204 mM^?1 s^?1), and bright luminescence under 1 cm chicken breast tissue.     

Ultraviolet upconversion fluorescence of Er3+ in Yb3+/Er3+-codoped Gd2O3 nanotubes

Under 980 nm excitation, room-temperature ultraviolet (UV) upconversion (UC) emissions of Er3+ from the 4G(9/2), 2K(13/2), and 2P(3/2) states were observed in Gd2O3:Yb3+/Er3+ nanotubes, which were synthesized via a simple wet-chemical route at low temperature and ambient pressure followed by a subsequent heat treatment at 800 degrees C. The experimental results exhibited that these UV emissions came from four-photon UC processes. In the Gd2O3:Yb3+/Er3+ nanocrystals, the energy transfers (ETs) from Yb3+ to Er3+ played important roles in populating the high-energy states of Er3+ ions. This material provides a possible candidate for building UV compact solid-state lasers or fiber lasers.     

Facile synthesis of β-NaYF4:Ln3+ (Ln = Eu, Tb, Yb/Er, Yb/Tm) microcrystals with down- and up-conversion luminescence

β-NaYF₄:Ln³⁺ (Ln = Eu, Tb, Yb/Er, Yb/Tm) hexagonal microrods have been successfully synthesized through a facile molten salt method without any surfactant. X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy, high-resolution transmission electron microscopy, and photoluminescence spectra were used to characterize the samples. It is found that at a preferred reaction temperature of 400 °C, the structure of β-NaYF₄ can gradually transform from microtubes to microrods as reaction time extends from 0.5 to 4 h. Furthermore, as the molar ratio of NaF:RE³⁺ (RE represents the total amount of Y³⁺ and the doped rare earth elements such as Eu³⁺, Tb³⁺, Yb³⁺/Er³⁺, or Yb³⁺/Tm³⁺) increased, the phase of sample transforms from YF₃ into NaYF₄. Under the excitation of 395 nm ultraviolet light, β-NaYF₄:5 %Eu³⁺ shows the emission lines of Eu³⁺ corresponding to ⁵D_0-3 → ⁷F _J (J = 1–4) transitions from 400 to 700 nm, resulting in red down-conversion (DC) light emission. When doped with 5 % Tb³⁺ ions, the strong DC fluorescence corresponding to ⁵D₄ → ⁷F _J (J = 6, 5, 4, 3) transitions with ⁵D₄ → ⁷F _J (green emission at 544 nm) being the most prominent group that has been observed. Moreover, upon 980 nm laser diode excitation, the Yb³⁺/Er³⁺- and Yb³⁺,Tm³⁺- co-doped β-NaYF₄ samples exhibit bright yellow and blue upconversion (UC) luminescence, respectively, by two- or three-photon UC process. The luminescence mechanisms for the doped lanthanide ions were thoroughly analyzed.     

Fabrication of Supported AuPt Alloy Nanocrystals with Enhanced Electrocatalytic Activity for Formic Acid Oxidation through Conversion Chemistry of Layer‐Deposited Pt2+ on Au Nanocrystals

The exploitation of nanoconfined conversion of Au‐ and Pt‐containing binary nanocrystals for developing a controllable synthesis of surfactant‐free AuPt nanocrystals with enhanced formic acid oxidation (FAO) activity is reported, which can be stably and evenly immobilized on various support materials to diversify and optimize their electrocatalytic performance. In this study, an atomic layer of Pt²⁺ species is discovered to be spontaneously deposited in situ on the Au nanocrystal generated from a reverse‐microemulsion solution. The resulting Au/Pt²⁺ nanocrystal thermally transforms into a reduced AuPt alloy nanocrystal during the subsequent solid‐state conversion process within the SiO₂ nanosphere. The alloy nanocrystals can be isolated from SiO₂ in a surfactant‐free form and then dispersedly loaded on the carbon sphere surface, allowing for the production of a supported electrocatalyst that exhibits much higher FAO activity than commercial Pt/C catalysts. Furthermore, by involving Fe₃O₄ nanocrystals in the conversion process, the AuPt alloy nanocrystals can be grown on the oxide surface, improving the durability of supported metal catalysts, and then uniformly loaded on a reduced graphene oxide (RGO) layer with high electroconductivity. This produces electrocatalytic AuPt/Fe₃O₄/RGO nanocomposites whose catalyst‐oxide‐graphene triple‐junction structure provides improved electrocatalytic properties in terms of both activity and durability in catalyzing FAO.     

Role of organic molecules on upconversion luminescence of LaF3 nanoparticles

Yb and Er codoped LaF₃ nanocrystals were synthesized and studied. The upconversion luminescence properties of nanocrystals capped with different ligands are mainly dependent on the ligands, especially for the red emission which is sensitive to the nonradiative relaxation. The chelation between the ligands and rare earth ions can affect the morphology and fluorescent properties of samples. The chelating ligands will reduce the nonradiative quenching by isolating the RE ions from surrounding environment. So the upconversion luminescence properties of the samples vary correspondingly.     

Rare earth ions and Ge nanocrystals in SiO(2)

Experimental studies of Ge nanocrystals embedded in SiO(2) films doped with Er and Yb deposited by rf-magnetron sputtering are presented. Although inter-band photoluminescence (PL) from the Ge nanocrystals is not observed, it is nevertheless found that the presence of Ge nanocrystals is crucial for obtaining light emission from Er(3+) and Yb(3+). For both kinds of rare earth ions, the intensity of the related PL line has a maximum after heat treatment at 800?°C, and the PL excitation spectra for the two cases are very similar. This suggests that the presence and the structure of the nanocrystals are important for the efficiency of PL from Er(3+) and Yb(3+). Experiments performed with multilayer structures of Ge nanocrystals and SiO(2) show that the optically active rare earth ions are located in the SiO(2) layers, and not inside the Ge nanocrystals. The mechanism of energy transfer from Ge nanocrystals to the rare earth ions is found to be non-optical.     

Fabrication of magnetic Fe3O4/C/TiO2 composites with nanotube structure and enhanced photocatalytic activity

Magnetic hybrid photocatalysts containing TiO₂ nanotube as outer catalytic layer and Fe₃O₄ as the core, with an amorphous carbon intermediate layer, were synthesised, characterised and applied to degradation of phenol under Xenon lamp irradiation. For the composite, Fe₃O₄/C microspheres were surrounded by anatase TiO₂ nanotubes with a diameter of ～8–10?nm. Photocatalytic performance of the Fe₃O₄/C/TiO₂ nanotube (FCT-NT) composites was also evaluated and showed enhanced activity superior to commercial P25 and homemade TiO₂ particles. The outstanding photocatalytic performance of FCT-NT sample could be attributed to its improved surface area and enhanced capability of optical absorption. Notably, the novel photocatalyst showed excellent magnetic behaviour and could be efficiently separated and collected from the wastewater.     

XRD EPR studies of ceramics Pr0.5Re0.5Ba2Cu3O7−δ in the orthorhombic and tetragonal phase

EPR, XRD, and magnetic studies are presented for Pr_0.5Re_0.5Ba₂Cu₃O_7?δ compounds (Re= La, Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Tm, Yb, and Lu) in the orthorhombic and tetragonal (large oxygen deficiency) phase. For the samples with Re=Dy, Ho, Y, Er, Tm, Yb, and Lu in the orthorhombic phase, the transition to the superconducting state has been observed in the temperatures rangeT _c between 18 and 40 K. For the samples with Nd and Yb in the tetragonal phase, EPR spectra coming from trivalent rare earth ions have been recorded. In the nonoxygenated sample Pr_0.5La_0.5Ba₂Cu₃O_7?δ the EPR spectrum arising from the non-Kramers trivalent praseodymium ion has been observed. A broad EPR line appearing in all our samples was attributed to superexchange interaction between copper ions over oxygen (O ₂ ^? ) bridges. Interestingly, for the Pr_0.5Re_0.5Ba_0.5Cu₃O_7?δ (Re = Er and Lu) compounds in the tetragonal phase at liquid-nitrogen temperature, a nonresonant microwave absorption in low magnetic fields has been detected.     

Fabrication of Novel Hierarchical Structured Fe3O4@LnPO4 (Ln=Eu,Tb, Er) Multifunctional Microspheres for Capturing and Labeling Phosphopeptides

Novel core–shell structured Fe₃O₄@LnPO₄ (Ln=Eu, Tb, Er) multifunctional microspheres with a magnetic Fe₃O₄ core and a LnPO₄ shell covered with spikes are synthesized for the first time through the combination of a homogeneous precipitation approach and an ion‐exchange process. Their potential for selective capture, rapid separation, and easy mass spectrometry (MS) labeling of the phosphopeptides from complex proteolytic digests are evaluated. These affinity microspheres can improve the specificity for capture of the phosphopeptides, realize fast magnetic separation, enhance the MS detection signals, and directly identify phosphopeptides through 80 Da mass loss in the mass spectra. The synthesis strategy could become a general and effective technique for similar core–shell hierarchical structures.     

Crystallization and spectroscopic properties in Er3+ doped oxyfluorogermanate glass ceramics containing Na

The Er³⁺ doped oxyfluorogermanate glasses, with a composition containing Na element, were synthesized by the conventional melting–quenching technique. When Na element was introduced into the composition of oxyfluorogermanate glass, the crystals behavior was investigated in details. Depending on the annealing procedure supplied, thermal annealing of precursor glasses in the system GeO₂/BaF₂/AlF₃/Na₂O/NaF/ZnO/GdF₃/ErF₃ led to the precipitation of different crystal phase nanocrystals. It was confirmed the nanocrystals in GC600 is orthorhombic NaBaAlF₆ which led to enhance obviously in the UC luminescence of Er³⁺. However, the nanocrystals in G585 led to decrease in the UC luminescence, which indicated few Er ions enter into the lattice of this nanocrystal phase. The reason of the decrease in UC emission intensity of GC585 was analyzed.     

Binary Superlattices from {Mo132} Polyoxometalates and Maghemite Nanocrystals: Long‐Range Ordering and Fine‐Tuning of Dipole Interactions

In the present article, the successful coassembly of spherical 6.2 nm maghemite (γ‐Fe₂O₃) nanocrystals and giant polyoxometalates (POMs) such as 2.9 nm {Mo₁₃₂} is demonstrated. To do so, colloidal solutions of oleic acid‐capped γ‐Fe₂O₃ and long‐chain alkylammonium‐encapsulated {Mo₁₃₂} dispersed in chloroform are mixed together and supported self‐organized binary superlattices are obtained upon the solvent evaporation on immersed substrates. Both electronic microscopy and small angles X‐ray scattering data reveal an AB‐type structure and an enhanced structuration of the magnetic nanocrystals (MNCs) assembly with POMs in octahedral interstices. Therefore, {Mo₁₃₂} acts as an efficient binder constituent for improving the nanocrystals ordering in 3D films. Interestingly, in the case of didodecyldimethylammonium (C₁₂)‐encapsulated POMs, the long‐range ordered binary assemblies are obtained while preserving the nanocrystals magnetic properties due to weak POMs–MNCs interactions. On the other hand, POMs of larger effective diameter can be employed as spacer blocks for MNCs as shown by using {Mo₁₃₂} capped with dioctadecyldimethylammonium (C₁₈) displaying longer chains. In that case, it is shown that POMs can also be used for fine‐tuning the dipolar interactions in γ‐Fe₂O₃ nanocrystal assemblies.     

Direct arc atomic emission analysis of yttrium,gadolinium, and neodymium oxides

The analytical potential of direct arc atomic emission detection of impurities in rare earth oxides (Y₂O₃, Cd₂O₃, and Nd₂O₃) on a Grand-Extra high-resolution spectrometer (VMK-Optoelektronika, Russia) is assessed. The conditions of analysis and spectrometer parameters are optimized. The detection threshold and lower limits for the content of a number of rare earth elements (Nd, Eu, Dy, Ho, Gd, Er, Tm, Yb, and Y) in these oxides are determined. The procedure for direct arc atomic emission analysis of yttrium, gadolinium, and neodymium oxides to detect rare earth impurities within the range of 0.001–0.1 wt % is elaborated; the procedure is characterized by improved metrological parameters compared to the standard method.