Magnetic properties of EuLn2O4 (Ln=rare earths)

Ternary rare earth oxides EuLn₂O₄ (Ln=Gd, Dy-Lu) were prepared. They crystallized in an orthorhombic CaFe₂O₄-type structure with space group Pnma. ¹⁵¹Eu Mössbauer spectroscopic measurements show that the Eu ions are in the divalent state. All these compounds show an antiferromagnetic transition at 4.2-6.3 K. From the positive Weiss constant and the saturation of magnetization for EuLu₂O₄, it is considered that ferromagnetic chains of Eu²⁺ are aligned along the b-axis of the orthorhombic unit cell, with neighboring Eu²⁺ chains antiparallel. When Ln=Gd-Tm, ferromagnetically aligned Eu²⁺ ions interact with the Ln³⁺ ions, which would overcome the magnetic frustration of triangularly aligned Ln³⁺ ions and the EuLn₂O₄ compounds show a simple antiferromagnetic behavior.     

Effect of crystal structure and ions concentration on luminescence in Yb and Tm codoped fluoride microcrystals

A facile hydrothermal method is used for the preparation of Tm³⁺/Yb³⁺ codoped fluoride microphosphors. The effect of crystal structure and ions concentration on the spectra and lifetimes of the radiative levels of Tm³⁺ ions in the different fluoride microcrystals is studied in detail. XRD analysis of Tm³⁺/Yb³⁺ codoped LaF₃ microcrystals shows that 20% Yb³⁺ doping is sufficient for hexagonal LaF₃ microparticles to crystallize completely in the orthorhombic phase. And lifetime analysis suggests that the average lifetimes of the radiative levels of Tm³⁺ ions increased when the matrix phase structure changing from orthorhombic phase to hexagonal phase with ytterbium dopant concentration changing.     

Electrochemical Behavior of the LaF3:Eu2+/Me Interface (Me = Sm,Ce, Gd,V, Ag)

The electrochemical behavior of the LaF₃ : Eu²⁺| interface (Me = Sm, Ce, Gd, V, Ag) is studied using stripping voltammetry. Current–voltage curves for cells Ag, AgCl|KCl and KF|LaF₃ : Eu²⁺|Sm (or Ce) may be viewed as background curves for analyzing solid-phase reactions with other metallic electrodes. The substrate material is found to affect properties of interfaces LaF₃ : Eu²⁺/Gd (or V), which are characterized either by solid-phase reactions involving the fluoride ion of a solid electrolyte or by reactions involving oxygen. Regularities, obtained for silver in contact with LaF₃ : Eu²⁺, link electrochemical signals of the reaction of the silver fluoride formation with the contact area.     

Oxygen reduction at the interface of nonstoichiometric fluoride single crystals with metal electrodes

Electrochemical measurements are carried out on three-phase boundaries LaF₃:Eu²⁺/Me, oxygen gas, where Me = Ti, Be, Ta, Au and also on the boundaries of CeF₃:Sr²⁺ with Ag-supported Ag and Bi microelectrodes by the methods of linear scan voltammetry, chronoamperometry, and cyclic voltammetry. The conditions beneficial for reduction of oxygen gas, transformations of chemisorbed oxygen, and the appearance of its mobile forms are considered. Results on the interaction of gaseous oxygen with metals in contact with LaF₃:Eu²⁺ single crystals are generalized. The correlation is found between the oxygen reduction potential and the difference of electronegativities Δχ Me-O. The relationship is revealed between the oxygen reduction potential and the Me-Me bond energy by taking into account the structural factor f/k _n, where f is the number of binding electrons and k _n is the coordination number.     

Effect of the Electrode Material on the Reduction of La<Superscript>3+</Superscript> and Ce<Superscript>3+</Superscript> in Fluoride-Conducting Solid Electrolytes

The reduction of immobile cations La³⁺ and Ce³⁺ in fluoride-conducting solid electrolytes (FSE) LaF₃ (Eu²⁺ 0.8 mol %), LaF₃ (Sr²⁺ 5 mol %), and CeF₃ (Sr²⁺ 5 mol %) in contact with Ag, Bi, Si, La, Ce, and Sm working electrodes is studied by chronoamperometry and voltammetry with linear potential scan. Discovered is linear dependence of initial segments of potentiostatic transients of cathodic current on t ^1/2 at FSE interfaces with Ag, Bi, La, Ce, and Sm. The dependence is due to diffusion-controlled instantaneous nucleation of Ln and Ce. The La³⁺ and Ce³⁺ reduction at the FSE/Ag interface is reversible in a narrow region. The reduction and oxidation of La³⁺ and Ce³⁺ (cations of the FSE rigid lattice) at the FSE/Me (Me = La, Ce and Sm, Bi, Si) interface is irreversible and involves a chemical reaction.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 662–672.Original Russian Text Copyright © 2005 by Turaeva, Kot, Urchukova, Murin.     

Phase diagrams of systems SrF2(Y,Ln)F3. II. Fusibility of systems and thermal behavior of phases

The phase diagrams of 14 SrF₂(Y,Ln)F₃ systems are given, where Ln are all the lanthanides except Pm and Eu. The diagrams have been constructed for temperature intervals from 850°C to the melting points according to the thermal and X-ray analysis. The fusibility diagrams for 12 systems have been obtained for the first time. The oxygen content in the specimens before and after thermal treatment was checked. The thermal behavior of the three types of solid solutions has been studied: (1) with the fluorite-type defective structure and its derivatives; (2) with the defective structure of the lanthanum fluoride, and (3) α-YF₃(α-UO₃) types. Maxima reflecting a noticeable effect of thermal stabilization on the fluorite-type structure by the heterovalent isomorphous substitution have been found for the majority of systems (with Ln = LaHo). The Sr_1?xLn_xF_2+x nonstoichiometric fluorite phases are formed in all the systems. Similar maxima corresponding generally to irrational compositions are present on the fusibility curves of the Ln_1?ySr_yF_3?y nonstoichiometric phases with the LaF₃-type structure (tysonite). Tysonite solid solutions are in all the systems, too. Nonstoichiometric phases with the α-YF₃-type structure are formed in the systems with Ln = ErLu. They are decomposed in the process of cooling and are the most unstable. The structure of the phase diagrams in the regions adjacent to lanthanide trifluorides are determined by polymorphism and morphotropy of the above-named compounds. Changes in the thermal stability of the nonstoichiometric phases and double chemical compounds in the series of lanthanides have been observed. The SrF₂(Y,Ln)F₃ systems studied give examples of the formation of phases with the highest concentrations of point defects among all the known binary fluoride systems (up to 50 at.%). The thermal stabilization effect of the nonstoichiometric phases with the fluorite structure results in the fact that the series of the two-component compositions is melted at considerably higher temperatures as compared with scandium fluoride, the most refractory single-component fluoride compound. This effect leads to formation of tysonite-type solid solutions with melting points exceeding 1500°C (mp of LaF₃—the most refractory fluoride material with tysonite-type structure).     

不同形貌YF_3微米晶的水热合成及YF_3:Eu~(3+)荧光性质(英文)

水热条件下,Y(NO3)3·6H2O分别与K2SiF6、KPF6反应得到了不同形貌的YF3(八面体及椭球形)。以X射线光电子能谱(XPS)检测了产物的化学组成,表明产物中只含有Y和F。X射线衍射(XRD)结果表明所得的产物均为正交晶系。扫描电子显微镜(SEM)和透射电子显微镜(TEM)对产物的表征结果指明八面体形YF3棱长为200nm,而椭球形YF3是由小的纳米块自组装而成。还研究了Eu3+掺杂后YF3的荧光性质,并提出了可能的形成机理。     

Photoluminescence properties of rare earths (Eu3+, Tb3+, Dy3+ and Tm3+) activated NaInW2O8 wolframite host lattice

The photoluminescence (PL) studies on NaIn_1?xRE_xW₂O₈, with RE=Eu³⁺, Tb³⁺, Dy³⁺ and Tm³⁺ phases have shown that the relative contribution of the host lattice and of the intra-f–f emission of the activators to the PL varies with the nature of the rare earth cation. In the case of Dy³⁺ and Tm³⁺ activators, with yellow and blue emission, respectively, the energy transfer from host to the activator plays a major role. In contrast for Eu³⁺, with intense red emission, the host absorption is less pronounced and the intra-f–f transitions of the Eu³⁺ ions play a major role, whereas for Tb³⁺ intra-f–f transitions are only observed, giving rise to green emission.     

Synthesis of highly fluorescent LaF3:Ln/LaF3 core/shell nanocrystals by a surfactant-free aqueous solution route

A surfactant-free aqueous solution route has been established for the synthesis of LaF₃:Ln³⁺/LaF₃ core/shell nanocrystals (Ln=Ce, Tb, Nd) heated at 75 °C at ambient pressure. All the as-prepared nanocrystals with spherical shape have an average size around 20 nm, and consist of well crystallized hexagonal phases. The X-ray photoelectron spectra was used to confirm that the LaF₃ shells have coated the LaF₃:Ce³⁺, Tb³⁺ cores. Compared with that of the original cores under the same conditions, the emission intensity of the LaF₃:Ce³⁺, Tb³⁺/LaF₃ and LaF₃:Nd³⁺/LaF₃ core/shell nanocrystals increased significantly of 120% and 60%, respectively. The quantum yield of the LaF₃:Ce³⁺, Tb³⁺/LaF₃ core/shell nanocrystals reached about 27% in aqueous solution. These results indicate that a significant reduction of the quenching from the surface of the core nanocrystals can be obtained by the synthesis of the core/shell structures, and this method can provide more desirable lanthanide-doped nanocrystals for potential biological applications.     

Thermal annealing of LaF3:Eu3+ nanocrystals synthesized by a solvothermal method and their luminescence properties

In this work, we used a low temperature solvothermal method to synthesize Eu³⁺-doped LaF₃ (LaF₃:Eu³⁺) nanocrystals. The effect of thermal annealing on their phase structures and luminescence properties was studied. Transformation from LaF₃ to LaOF was observed after the annealing, and the initial transformation process was studied using a rapid thermal annealing technique. It was found that a sufficiently high annealing temperature is required for the transformation of LaF₃ to LaOF. LaOF phase started to be formed after annealing at 500 °C for as short as 5 min, and higher annealing temperatures and longer annealing time led to a larger amount of LaOF formed. With the increase of the formation of LaOF, the luminescence was greatly enhanced. Strong O^2? → Eu³⁺ charge transfer band was present in these samples annealed at 500 °C and higher temperatures, and greatly enhanced ⁷F₀ → ⁵D₂ transition of Eu³⁺ was also observed.     

Synthesis,Persistent Luminescence,and Thermoluminescence Properties of Yellow Sr3SiO5:Eu2+,RE3+ (RE=Ce,Nd, Dy,Ho, Er,Tm, Yb) and Orange‐Red Sr3−xBaxSiO5:Eu2+, Dy3+ Phosphor

Sunlight‐excitable orange or red persistent oxide phosphors with excellent performance are still in great need. Herein, an intense orange‐red Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ persistent luminescence phosphor was successfully developed by a two‐step design strategy. The XRD patterns, photoluminescence excitation and emission spectra, and the thermoluminescence spectra were investigated in detail. By adding non‐equivalent trivalent rare earth co‐dopants to introduce foreign trapping centers, the persistent luminescence performance of Eu²⁺ in Sr₃SiO₅ was significantly modified. The yellow persistent emission intensity of Eu²⁺ was greatly enhanced by a factor of 4.5 in Sr₃SiO₅:Eu²⁺,Nd³⁺ compared with the previously reported Sr₃SiO₅:Eu²⁺, Dy³⁺. Furthermore, Sr ions were replaced with equivalent Ba to give Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ phosphor, which shows yellow‐to‐orange‐red tunable persistent emissions from λ=570 to 591 nm as x is increased from 0 to 0.6. Additionally, the persistent emission intensity of Eu²⁺ is significantly improved by a factor of 2.7 in Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ (x=0.2) compared with Sr₃SiO₅:Eu²⁺,Dy³⁺. A possible mechanism for enhanced and tunable persistent luminescence behavior of Eu²⁺ in Sr_3?xBa_xSiO₅:Eu²⁺,RE³⁺ (RE=rare earth) is also proposed and discussed.     

Visible and near-IR luminescence via energy transfer in rare earth doped mesoporous titania thin films with nanocrystalline walls

Selected photoluminescence in the wavelength range of 600-1540 nm is generated by energy transfer from a light-gathering mesostructured host lattice to an appropriate rare earth ion. The mesoporous titania thin films, which have a well-ordered pore structure and two-phase walls made of amorphous titania and TiO₂ nanocrystallites, were doped with up to 8 mol% lanthanide ions, and the ordered structure of the material was preserved. Exciting the titania in its band gap results in energy transfer and it is possible to observe photoluminescence from the crystal field states of the rare earth ions. This process is successful for certain rare earth ions (Sm³⁺, Eu³⁺, Yb³⁺, Nd³⁺, Er³⁺) and not for others (Tb³⁺, Tm³⁺). A mechanism has been proposed to explain this phenomenon, which involves energy transfer through surface states on titania nanocrystals to matching electronic states on the rare earth ions.     

Effect of the electrode material on the oxygen reduction at the nonstoichiometric lanthanum fluoride/electrode interface

The voltammetry method with a linear potential scan is used for investigating the effect the electrode material (Ni, Co, electrodes on the basis of cobalt oxides modified with carbon) exerts on the reduction of gaseous oxygen at interfaces solid fluoride-conducting electrode LaF₃:Eu²⁺/electrode, O₂, and conjugated processes. Properties of the modified electrodes are characterized by the impedance spectroscopy, scanning electron microscopy, and x-ray photoelectron spectroscopy methods. The oxygen reaction is irreversible at the LaF₃:Eu²⁺|Ni (or Co) interfaces. At the interface of LaF₃:Eu²⁺ with modified electrodes Co (C n at %), where n = 5 and 9, mobile forms of oxygen are reversible and the reduction of gaseous and chemisorbed oxygen is controlled by diffusion with different effective kinetic parameters.     

Solubility enhancement of Nd7+ in scandium-substituted rare earth-aluminum garnets

An increased solubility of Nd³⁺ in YAG has been achieved by means of expansion of its crystal lattice with Sc³⁺ ions substituting for Al³⁺ ions in the octahedral sites. A number of other scandium substituted rare earth aluminum garnets of general formula {R₃}[Sc₂](Al₃)O₁₂ have been prepared and results are compared with similar compounds in {R₃}[Sc₂](Fe₃)O₁₂ systems. It is shown that the expansion of the YAG lattice by octahedral substitution significantly increases the solubility of Nd³⁺ on dodecahedral sites. The results of substitution of Sc in other rare earth-aluminum systems appear to be consistent with results obtained in the yttrium-aluminum system and so ions bigger than Gd³⁺, such as Eu³⁺ and Sm³⁺, can form garnets {Eu₃}[Sc₂](Al₃)O₁₂ and {Sm₃}[Sc₂](Al₃)O₁₂.     

An Unusual Valence State: Trivalent Europium in Intermetallic Eu2Ir3Al9

Eu₂Ir₃Al₉, synthesized from the elements in tantalum tubes, is one of the rare examples for trivalent europium in the field of intermetallic compounds. The compound crystallizes in the Y₂Co₃Ga₉-type structure (space group Cmcm), with lattice parameters fitting in between the isostructural samarium and gadolinium compounds. In the crystal structure, the Eu atoms form Al₃-triangle-centered honeycomb layers and exhibit a coordination number of 17 in the shape of a fivefold-capped hexagonal prism (Eu@Ir₆Al₆+Al₅). Magnetic measurements indicate an overall low susceptibility, in line with van Vleck paramagnetism caused by the Eu³⁺ cations. Fits of the susceptibility yield a coupling constant of λ=290(10) K and an effective magnetic moment of μ_eff=4.56(1) μ_B, in line with a slight hybridization of the ⁷F₀ and ⁷F₁ state. ¹⁵¹Eu Mössbauer spectroscopic investigations unambiguously prove the presence of solely Eu³⁺ in the bulk material.     

Galvanostatic investigation of electrochemical processes at the LaF<Subscript>3</Subscript>/M (M: Ag,Bi) interface

The electrochemical processes at the interface between solid fluorine-conducting electrolyte LaF₃(Eu²⁺ 0.8 mol %) and silver or bismuth electrodes in the two-electrode cell with nonpolarizable reference electrode are studied using the galvanostatic method. The anodic galvanostatic transients of LaF₃: Eu²⁺/Ag and LaF₃: Eu²⁺/Bi interfaces are linearized on the log(η ? η_max), vs. t coordinates, i.e. the rate of LaF₃|MF _n |M electrode formation is limited by slow surface diffusion of metal adions. The initial portions of cathodic galvanostatic transients in the range of solid-electrolyte lanthanum reduction are approximated by the linear dependence of η on log(1 ? √t/τ). The plots of logI vs. 1/η are linear both for the lanthanum reduction and for silver and bismuth oxidation involving mobile fluoride ion of solid electrolyte, which is typical for two-dimensional growth of new phase.     

Conductivity of nonstoichiometric fluorides LnF2+x (Ln = Sm,Eu, Yb)

Nonstoichiometric fluorides LnF_2+x (Ln = Sm, Eu, Yb) were synthesized by reduction of trifluorides with the above rare-earth elements. The resulting phases were identified by chemical and X-ray phase analyses, their composition and structure were determined, and their lattice constants were found. The ac bridge method at a frequency of 70 kHz was used to study the conductivity of the synthesized compounds and starting trifluorides in the temperature range 773–298 K. The temperature dependence of the conductivity of these compounds is satisfactorily approximated by the Arrhenius-Frenkel equation. A kink is observed on the plots of the electrical conductivity against temperature for all compounds. With decreasing content of fluorine, this kink shifts to higher temperatures. The highest conductivity is observed for the phases with low crystal packing density. With increasing content of fluorine, the conductivity of all nonstoichiometric phases not belonging to substitution solid solutions approaches the conductivity of the corresponding trifluorides.     

Über die verbreitung ternärer komplexnitride mit Perowskitstruktur in SE-Al-N-systemen (SE ≡ La,Ce, Pr,Nd, Sm,Gd, Tb,Dy, Ho,Er, Tm,Yb, Lu)

The existence of complex nitrides in the RE-Al-N (RE ≡ rare earth) ternaries is investigated. In the systems containing lanthanum, cerium, praseodymium, neodymium and samarium either ternary phases (RE)₃AlN_x with a perovskite-type structure or alternatively almost complete filling of the octahedral voids by nitrogen in (RE)₃Al phases with an L1₂-type structure are found. An isothermal section for Pr-Al-N at 600 °C is presented. In the systems RE-A1-N (RE ≡ Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) no ternary phase is observed.     

Structural aspects and defect chemistry in In2O3

The C-type rare earth structure of In₂O₃ is compared with the fluorite structure. The stability of the structure is discussed based on DTA and X-ray work and electron microscopy. Ordering of defects does not take place, so that defect chemistry can be formulated for isolated defects in nonstoichiometric In₂O₃. The influence of the incorporation of aliovalent cations into the In₂O₃ host lattice is discussed and a defect model is suggested.     

Phase‐ and Size‐Controllable Synthesis of Hexagonal Upconversion Rare‐Earth Fluoride Nanocrystals through an Oleic Acid/Ionic Liquid Two‐Phase System

Herein, we introduce a facile, user‐ and environmentally friendly (n‐octanol‐induced) oleic acid (OA)/ionic liquid (IL) two‐phase system for the phase‐ and size‐controllable synthesis of water‐soluble hexagonal rare earth (RE=La, Gd, and Y) fluoride nanocrystals with uniform morphologies (mainly spheres and elongated particles) and small sizes (<50 nm). The unique role of the IL 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BmimPF₆) and n‐octanol in modulating the phase structure and particle size are discussed in detail. More importantly, the mechanism of the (n‐octanol‐induced) OA/IL two‐phase system, the formation of the RE fluoride nanocrystals, and the distinctive size‐ and morphology‐controlling capacity of the system are presented. BmimPF₆ is versatile in term of crystal‐phase manipulation, size and shape maintenance, and providing water solubility in a one‐step reaction. The luminescent properties of Er³⁺‐, Ho³⁺‐, and Tm³⁺‐doped LaF₃, NaGdF₄, and NaYF₄ nanocrystals were also studied. It is worth noting that the as‐prepared products can be directly dispersed in water due to the hydrophilic property of Bmim⁺ (cationic part of the IL) as a capping agent. This advantageous feature has made the IL‐capped products favorable in facile surface modifications, such as the classic Stober method. Finally, the cytotoxicity evaluation of NaYF₄:Yb,Er nanocrystals before and after silica coating was conducted for further biological applications.