Ba2.2Ca0.8Mg4F14, a new “solid solution stabilized” matrix for an intense blue phosphor

Barium calcium magnesium fluoride (Ba₂(Ba_xCa_1‐x)Mg₄F₁₄, x=0.19‐0.26) has been synthesized at 850 °C from precursors prepared by the solution precipitation method. Single crystals with composition of Ba_2.200(2)Ca_0.800(2)Mg₄F₁₄were obtained after prolonged heating. Lattice parameters from single crystal data are a = 12.4203(8) and c = 7.4365(5) Å [tetragonal, space group P4₂/mnm (No. 136)]. They increase with increasing barium concentration within a given stability window. The structure is built of a network of MgF₆ octahedra forming a pyrochlore related channel system and isolated fluorine ions. Within the channels, heavy alkaline earth ions are located. The wide channel is filled with off‐center positioned barium ions. The channel with a narrow cross section hosts both ions, Ca²⁺and Ba²⁺. The structure is isotypic with Pb₃Nb₄O₁₂F₂ but has a different coordination around Ba/Ca and Pb, respectively. Doped with ∼1% Eu(II), the compound shows intense blue luminescence under UV activation. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Defect structure and ionic conductivity of Ca1 ? xScxF2 + x (0.02 ≤ x ≤ 0.15) single crystals

Single crystals of the Ca_{1 − x} Sc _x F_{2 + x} (x = 0.106, 0.132, 0.156) solid solutions (CaF₂ structure type, space group Fm m) are investigated using X-ray diffraction. It is revealed that the crystals under investigation contain vacancies in the 8c positions and interstitial fluorine ions in the 48i positions. The coordination number of Sc³⁺ ions in the structure of the Ca_{1 −x} Sc _x F_{2 + x} solid solutions is equal to eight. The specific features of the concentration dependences of the ionic conductivity and the activation energy of ion transfer for the Ca_{1 − x} Sc _x F_{2 + x} (0.02 ≤ x ≤ 0.15) solid solutions are explained in the framework of the percolation model of conducting “defect regions.” The percolation threshold equal to 3–5 mol % ScF₃ corresponds to the model of [Ca_{14 − n} Sc _n F₆₈] octacubic clusters containing fluorine ions in the 48i positions. The ionic conductivity of the Ca_{1 − x} Sc _x F_{2 + x} solid solutions is analyzed in comparison with the change in this characteristic for the series of Ca_0.8 R _0.2F_2.2 crystals with rare-earth elements. Original Russian Text ? E.A. Sulyanova, V.N. Molchanov, N.I. Sorokin, D.N. Karimov, S.N. Sulyanov, B.P. Sobolev, 2009, published in Kristallografiya, 2009, Vol. 54, No. 4, pp. 612–622.     

Ionic conductivity of congruently melting Ca0.6Sr0.4F2 and Ca1 ? x ? ySryRxF2 + x (R = La, Ce, Pr, Nd) single crystals with fluorite structure

Single crystals of congruently melting compositions of the Ca_0.6Sr_0.4F₂ and Ca_{1 − x − y} Sr _y R _x F_{2 + x} (R = La, Ce, Pr, Nd; x = 0.16–0.21; y = 0.07–0.16) solid solutions with fluorite structure have been grown by the Bridgman-Stockbarger method. Their electrical properties have been investigated in the range from 473 to 823 K, and it is shown that they are ionic conductors. For Ca_0.6Sr_0.4F₂ crystals, the ionic conductivity σ = 2 × 10⁻⁶ S/cm at 673 K, and the ion transport activation energy E _a = 1.1 eV. For Ca_0.77Sr_0.07La_0.16F_2.16, Ca_0.70Sr_0.11Ce_0.19F_2.19, Ca_0.65Sr_0.15Pr_0.20F_2.20, and Ca_0.58Sr_0.21Nd_0.21F_2.21 crystals, the values of σ lie in the range from 9 × 10⁻⁷ to 2 × 10⁻⁶ S/cm at 500 K, and the activation energy E _a is 0.88–0.93 eV. The concentration and mobility of ionic charge carriers in Ca_{1 − x − y} Sr _y R _x F_{2 + x} crystals have been calculated. Original Russian Text ? N.I. Sorokin, D.N. Karimov, E.A. Krivandina, Z.I. Zhmurova, O.N. Komar’kova, 2008, published in Kristallografiya, 2008, Vol. 53, No. 2, pp. 297–303.     

Single crystals of the fluorite nonstoichiometric phase Eu 0.9162+ Eu 0.0843+ F2.084 (conductivity, transmission, and hardness)

The nonstoichiometric phase EuF_2+x has been obtained via the partial reduction of EuF₃ by elementary Si at 900–1100°C. Eu_0.916²⁺Eu_0.084³⁺F_2.084 (EuF_2.084) single crystals have been grown from melt by the Bridgman method in a fluorinating atmosphere. These crystals belong to the CaF₂ structure type (sp. gr. Fm $ \bar 3 $ \bar 3 m) with the cubic lattice parameter a = 5.8287(2) ?, are transparent in the spectral range of 0.5–11.3 μm, and have microhardness H _μ = 3.12 ± 0.13 GPa and ionic conductivity σ = 1.4 × 10⁻⁵ S/cm at 400°C with the ion transport activation energy E _a = 1.10 ± 0.05 eV. The physicochemical characteristics of the fluorite phases in the EuF₂ − EuF₃ systems are similar to those of the phases in the SrF₂ − EuF₃ and SrF₂ − GdF₃ systems due to the similar lattice parameters of the EuF₂ and SrF₂ components. Europium difluoride supplements the list of fluorite components MF₂ (M = Ca, Sr, Ba, Cd, Pb), which are crystal matrices for nonstoichiometric (nanostructured) fluoride materials M _{1 − x} R _x F_{2 + x} (R are rare earth elements).     

Growth and defect crystal structure of CdF2 and nonstoichiometric Cd1?xRxF2+x phases (R = rare earth and In). Part 3. Crystal structure of as-grown Cd0.90R0.10F2.10 (R = Sm-Lu, Y) single crystals

The structures of as-grown Cd_0.90 R _0.10F_2.10 (R = Sm-Lu and Y) crystals are determined and related to the CaF₂ structure type. It is assumed that in all the crystals R ³⁺ and Cd²⁺ ions form clusters with the tetrahedral configuration of the [Cd₂ R ₂F₂₆] and [CdR ₃F₂₆] cations. The concentration of [Cd₂ R ₂F₂₆] cations in crystals with R = Er-Lu and Y is considerably higher that in crystals with R = Sm-Ho. The tendency to a decrease in the coordination number of R ³⁺ toward the end of the rare earth series manifests itself in the fact that the Yb³⁺ ions in Cd_0.90Yb_0.10F_2.10 occupy both tetrahedral (c.n. 10) and octahedral (c.n. 8) clusters. The Yb³⁺ ions in tetrahedral clusters are displaced from their basic positions by 0.15 Å along the 〈100〉 directions. In Cd_1−x R _x F_2+x the relaxation of the anion sublattice of the fluorite matrix around clusters is much more pronounced than in the Ca_1−x R _x F_2+x phases having similar geometry. __________ Translated from Kristallografiya, Vol. 50, No. 2, 2005, pp. 235–248. Original Russian Text Copyright ? 2005 by Sul’yanova, Shcherbakov, Molchanov, Simonov, Sobolev.     

Controlled chemical co-precipitation and solid phase synthesis,microstructure and photoluminescence of La3PO7:Eu3+ phosphors

Eu³⁺-doped oxy-phosphate (La₃PO₇:Eu³⁺) with monoclinic phase has been synthesized via solid phase and co-precipitation methods. The products present various regular morphologies after high temperature thermal treatment, such as bulk with holes, leaf-like flake, nano-rod and so on. All the phosphors exhibit the characteristic fluorescence of Eu ion, the electric dipole transition ⁵D₀→⁷F₂ of Eu³⁺ ions is dominant indicating that the sites of Eu³⁺ ions in La₃PO₇ have no the inversion center. Furthermore, the intensity of ⁵D₀→⁷F₂ increases due to the introducing of surfactant and increasing of the calcination temperature.     

Structure and features of the surface morphology of <Emphasis Type="Italic">A</Emphasis><Superscript>4</Superscript><Emphasis Type="Italic">B</Emphasis><Superscript>6</Superscript> chalcogenide epitaxial films

The structure and features of the surface morphology of Pb_{1 − x} Mn _x Se (x = 0.03) epitaxial films grown on freshly cleaved BaF₂(111) faces and PbSe_{1 − x} S _x (100) (x = 0.12) single-crystal wafers were investigated by molecular beam condensation and the hot-wall method. It is shown that the epitaxial films, in accordance with the data in the literature for other chalcogenides, grow in the (111) and (100) planes, repeating the substrate orientation. Black aggregates are observed on the film surface of the films grown. The results obtained are compared with the data in the literature and generalized for other chalcogenides: A ⁴ B ⁶:Pb (S, Se, Te); Pb_{1 − x} Sn _x (S, Se, Te); and Pb_{1 − x} Mn (Se, Te). It is established that the formation of black aggregates, which are second-phase inclusions on the surface of epitaxial films obtained by vacuum thermal deposition, is characteristic of narrow-gap A ⁴ B ⁶ chalcogenides.     

Investigation of Trimetallic Ligand-Pillared Oxyfluorides: Ag2Cu(pzc)2MOxF6?x (M?=?Mo, Nb, and W)

Abstract  

Three new ligand-pillared hybrid solids, Ag₂Cu(pzc)₂MO _x F_6−x (I, M = Mo, x = 2; II, M = W, x = 2; III, M = Nb, x = 1) (pzc = pyrazine-2-carboxylate) were synthesized via hydrothermal reactions at 150 °C, and their structures were determined by single-crystal X-ray diffraction (P2₁/n (No. 14), Z = 2; a = 7.2302(1), 7.2124(2), 7.2715(2) ?; b = 7.9460(1), 7.9270(2), 7.98436(3) ?; c = 13.9173(2), 13.8959(4), 13.8226(5) ?, for I, II, and III, respectively). All three are isostructural and contain unusual trimetallic (Ag₂CuMO _x F_6−x )²⁺ layers that consist of [Ag₂O₂F₂] _n and [CuMO _x F_6−x ] _n chains that alternate within the layers. Each structure also contains [MO _x F_6−x ]²⁻ octahedra with fully disordered O/F positions and with an inversion center on the M ⁿ⁺ sites, i.e., Mo⁶⁺, W⁶⁺ and Nb⁵⁺. Magnetic susceptibility measurements can be fitted to the Curie–Weiss law with a Curie constant consistent with a single non-interacting Cu(II) (S = ?) site per formula unit. Thermogravimetric analyses indicate that these hybrid compounds are stable up to ~280 °C, with each exhibiting a single weight-loss step beginning at ~300 °C that corresponds to the loss of all pyrazine-2-carboxylate ligands and additional O/F atoms via oxidation of the ligand during its removal. UV–Vis diffuse reflectance measurements show that each exhibits an optical bandgap size of ~2.8 eV, and which electronic-structure calculations show arise from excitations between the Cu(II)-based valence orbitals and the M^5+/6+-based conduction band orbitals.     

Nanostructured crystals of fluorite phases Sr1 ? xRxF2 + x (R are rare-earth elements) and their ordering: IV. Study of the optical transmission spectra in the 2–17-μm wavelength range

Transmission spectra of two-component crystals of Sr_1−x R _x F_2+x (R = Y, La-Lu; 0 ≤ x ≤ 0.5) in the 1–17-μm wavelength range were studied. The spectral characteristics of these crystals and of single-component crystals of MF₂ (M = Ca, Sr, or Ba) and RF₃ (R = La-Nd) were compared. The transmission cutoff of Sr_1−x R _x F_2+x crystals is shifted to shorter wavelengths with increasing x. The same tendency is observed with the increasing atomic number R of rare-earth elements for two isoconcentration series of Sr_1−x R _x F_2+x (x ∼ 0.10 and 0.28). This tendency is pronounced at large x. The transmission cutoff of Sr_1−x R _x F_2+x crystals can be varied in the range of from 10.7 to 12.2 μm by changing their qualitative (R) and quantitative (x) composition. Hence, these crystals can be assigned to multicomponent fluoride optical materials with controlled optical characteristics. The Sr_1−x R _x F_2+x crystals, where R = Ce-Sm, were shown to be promising materials for the design of selective optical filters in the 2–10-μm spectral range.     

Nanostructured crystals of Sr1?xRxF2+x fluorite phases and their ordering: 6. Microindentation analysis of crystals

Hardness, crack resistance, brittleness, and effective fracture energy have been studied for crystals of 24 fluorite phases Sr_{1 − x} R _x F_{2 + x} (R are 14 rare earth elements (REEs); 0 < x ≤ 0.5) and SrF2 grown by the Bridgman method from a melt. These characteristics change nonlinearly with an increase in the REE content for Sr_{1 − x} R _x F_{2 + x} (0 < x ≤ 0.5) with R = La, Nd, Sm, Gd, and Lu; it is maximum in the range x < 0.1 for all REEs. The changes in a number of REEs have been traced for an isoconcentration series of Sr_0.90 R _0.10F_2.10 crystals (R = La, Nd, Sm, Gd, Ho, Er-Lu, or Y) and crystals (similar in composition) with R = Tb and Dy. The hardness of Sr_{1 − x} R _x F_{2 + x} crystals is higher by a factor of ∼2–3 than that of SrF2. The effect of decrease in microstresses in SrF₂ crystals is confirmed by the isomorphic introduction of R ³⁺ ions into this crystalline matrix.     

Thermal Expansion of EuF<Subscript>2 + <Emphasis Type="Italic">x</Emphasis></Subscript> Single Crystals and Their Thermal Stability

Thermal expansion of an EuF_2.136 nonstoichiometric crystal with the fluorite structure type (Eu _0.864 ²⁺ Eu _0.136 ³⁺ F_2.136, lattice parameter 5.82171(5) Å) has been experimentally investigated in the temperature range of 9–500 K. The coefficient of thermal expansion is α = 15.8 × 10^–6 K^–1 at T = 300 K. The observed anomalies in the behavior of the coefficient of thermal expansion at T > 400 K are related to the oxidation processes with partition of Eu²⁺ ions. It is established by differential scanning calorimetry that the onset temperature of EuF_{2 + x} oxidation in air is 430 K and that this process occurs in three stages. X-ray diffraction analysis shows that the oxidation is accompanied by the formation of a phase mixture based on two modifications of the Eu _{1– y} ³⁺ Eu _y ²⁺ F_3–y solid solution with the structure types of tysonite (LaF₃), orthorhombic β-YF₃ phase, and europium oxyfluorides of variable composition EuO_1–xF_{1 + 2x}, with dominance of the latter.     

Mechanochemical synthesis of nonstoichiometric nanocrystals La1 ? yCayF3 ? y with a tysonite structure and nanoceramic materials from CaF2 and LaF3 crystals

The nonstoichiometric phases La_{1 − y} Ca _y F_{3 − y} (y = 0.15, 0.20) with a tysonite (LaF₃) structure have been prepared for the first time by the mechanochemical synthesis from CaF₂ and LaF₃ crystals. The average size of coherent scattering regions is approximately equal to 10–30 nm. It has been shown that the compositions of the phases prepared by the mechanochemical synthesis are inconsistent with the phase diagram of the CaF₂-LaF₃ system. The “mechanohydrolysis” of the La_{1 − y} Ca _y F_{3 − y} phase has been observed for the first time. Under these conditions, the La_{1 − y} Ca _y F_{3 − y} phase partially transforms into lanthanum calcium oxyfluoride for a milling time of 180 min with intermediate sampling. The La_{1 − y} Ca _y F_{3 − y} nanoceramic materials have been prepared from a powder of the mechanochemical synthesis product by pressing under a pressure of (2–6) × 10⁸ Pa at room temperature. The electrical conductivity of the synthesized materials at a temperature of 200°C is equal to 4.9(6) × 10⁻⁴ S/cm, and the activation energy of electrical conduction is 0.46(2) eV. These data for the nanoceramic materials coincide with those obtained for migration of fluorine vacancies in single-crystal tysonite fluoride materials. Original Russian Text ? B.P. Sobolev, I.A. Sviridov, V.I. Fadeeva, S.N. Sul’yanov, N.I. Sorokin, Z.I. Zhmurova, I.I. Khodos, A.S. Avilov, M.A. Zaporozhets, 2008, published in Kristallografiya, 2008, Vol. 53, No. 5, pp. 919–929.     

Molecular beam epitaxy of Ca1−xRxF2+x (R=Nd, Er) layers: study of RHEED pattern and lattice mismatch

Ca_1−xNd_xF_2+x and Ca_1−xEr_xF_2+x layers were grown on CaF₂(1 1 1) substrates at 600 and 550°C, respectively, by molecular beam epitaxy. Reflection high-energy electron diffraction (RHEED) investigation revealed that Ca_1−xNd_xF_2+x layers have two types of surface structure, namely (1×1) and ( )R30⁰ with hexagonal symmetry, depending on Nd mole fraction, while Ca_1−xEr_xF_2+x layers have three types of surface structure, namely (1×1) and (2×2) with hexagonal symmetry, and a triple rotated domain structure based on a rectangular cell depending on Er mole fraction. The lattice mismatch of the epilayers and substrate, which is important for applications involving buffer layers, was measured by X-ray rocking curve (XRC) analysis.     

Displacements in the cationic motif of nonstoichiometric fluorite phases Ba1 − x R x F2 + x as a result of the formation of {Ba8[R 6F68–69]} clusters: I. The Ba0.78Tm0.22F2.22 crystals

The displacements of Ba²⁺ cations in the cationic motif of Ba_0.78Tm_0.22F_2.22 crystals, which are representatives of nonstoichiometric fluorite phases Ba_{1 ? x} R _x F_{2 + x} , are proved for the first time with the use of precision investigations of the fine atomic structure. It is shown that the cation displacements, like the previously revealed displacements in the anionic motif, reflect the formation of {Ba₈[R ₆F_68–69]} superclusters of structural defects with nanometer linear sizes. The Ba ²⁺ cations are displaced from the fluorite crystallographic positions 4a (space group Fm $ \bar 3 The displacements of Ba²⁺ cations in the cationic motif of Ba_0.78Tm_0.22F_2.22 crystals, which are representatives of nonstoichiometric fluorite phases Ba_{1 − x} R _x F_{2 + x} , are proved for the first time with the use of precision investigations of the fine atomic structure. It is shown that the cation displacements, like the previously revealed displacements in the anionic motif, reflect the formation of {Ba₈[R ₆F_68–69]} superclusters of structural defects with nanometer linear sizes. The Ba ²⁺ cations are displaced from the fluorite crystallographic positions 4a (space group Fm m) to the positions 32f. The static nature of the cation displacements is confirmed by the fact that these displacements are retained at a temperature of 110 K. The correctness of the interpretation of the correlation between the cation displacements and the formation of superclusters of structural defects is supported by the coincidence of the intercationic distances determined in the disordered phase Ba_0.78Tm_0.22F_2.22 with those found in the previously studied ordered phases Ba₄ R ₃F₁₇ (R = Y, Yb). The model with splitting of cationic positions is appropriate for testing in structural investigations of crystals of the fluorite phases M _{1 − x} R _x F_{2 + x} at room temperature. Original Russian Text ? A.M. Golubev, L.P. Otroshchenko, V.N. Molchanov, B.P. Sobolev, 2008, published in Kristallografiya, 2008, Vol. 53, No. 6, pp. 1023–1030.     

Perovskite-like fluorides and oxyfluorides: Phase transitions and caloric effects

An analysis of the effect that chemical and hydrostatic pressures have on the thermodynamic properties of perovskite-like fluorine-oxygen compounds A ₂ A′MeO _x F_{6 − x} has revealed that materials under-going order-disorder transitions and having significant external-pressure compliance have the highest caloric efficiency. Some of the fluorides and oxyfluorides under study can be considered promising solid coolants.     

Mild hydrothermal synthesis and structures of mixed‐valence iron phosphates: SrFe3(PO4)3 and the interesting Mg2+‐doped AFe3 (PO4)3 (A = Ba,Pb) in Fe2+ site

Series of mixed valence monophosphates AFe_3‐xMg_x(PO₄)₃ [A = Sr(x = 0), Ba(x = 0.6), Pb(x = 0.6)] were synthesized by mild hydrothermal treatment at 210 °C. Refinements of single crystal X‐ray diffraction datas show all these compounds are isostructural. The attempts to make AFe₃(PO₄)₃ (A = Ba, Pb) hydrothermally in the experiment were unsuccessful. However, the Mg‐doped homologues AFe_2.4Mg_0.6(PO₄)₃ (A = Ba, Pb) were synthesized with the addition of MgCO₃ in the reactants as mineralizer. EDS and single crystal X‐ray data refinement indicated that the Mg²⁺ cations were doped in the Fe²⁺ sites of AFe_2.4Mg_0.6(PO₄)₃ (A = Ba, Pb). The influence of the Mg‐doping on the structure and the reason why the Mg doped in the Fe(II) site instead of A site was discussed from the point of view of the bond valence model.     

Growth and defect structure of CdF2 and nonstoichiometric Cd1?xRxF2 + x phases (R = rare earth elements and In). I. Growth of Cd1?xRxF2 + x single crystals (R = La-Lu, Y)

This article begins a series of publications on growth of single crystals of nonstoichiometric Cd_{1− x} R _x F_{2 + x} phases (R = La-Lu, Y, In) with the defect CaF₂-type structure, their crystal structures, and some properties. The present article is dedicated to the phase diagrams of the CdF₂-RF₃ systems in the region of Cd_1−x R _x F_{2 + x} formation. Their analysis shows that it is possible to synthesize homogeneous Cd_0.9 R _0.1F_2.1 crystals. The dependence of the defect structure of the crystals on the type and concentration of rare earth elements is studied on specially grown Cd_0.9 R _0.1F_2.1 (R = La-Lu) and Cd_1−x Y_xF_{2 + x} (x = 0.1, 0.15, 0.20) crystals. It is shown that, despite the fact that all the Cd_0.9 R _0.1F_2.1 crystals melted congruently, irrespectively of the rare earth elements used, they were rather homogeneous. The chemical compositions of the Cd_1−x R _x F_{2 + x} phases (R = Sm, Gd, Tb, Ho, and Lu) determined by the method of inductively coupled plasma atomic emission spectroscopy (ICP-AES) turned out to be close to Cd_0.9 R _0.1F_2.1. __________ Translated from Kristallografiya, Vol. 49, No. 3, 2004, pp. 566–574. Original Russian Text Copyright ? 2004 by Buchinskaya, Ryzhova, Marychev, Sobolev.     

Mechanochemical synthesis of nonstoichiometric fluorite Ca1?xLaxF2+x nanocrystals from CaF2 and LaF3 single crystals

The nonstoichiometric Ca_1−x La_xF_2+x phase (x ≥ 0.1) is obtained by mechanochemical synthesis from CaF₂ and LaF₃ single crystals. This phase is the first representative of fluorite fluorides obtained by mechanochemical synthesis in the MF_m-RF_n systems (m < n ≤ 4). The average grain size ranges within 10–30 nm. The temperature dependence of ionic conductivity of the mechanochemically synthesized phase pressurized at 600 MPa (at its high-temperature portion at temperatures exceeding 200–250°C) coincides with the conductivity of the single crystals of the same composition (Ca_0.8La_0.2F_2.2). The activation energy of ionic conductivity (0.95 eV) corresponds to migration of interstitial fluoride ions in the crystal bulk. Mechanochemical synthesis of a multicomponent fluoride material with nanometer grains opens a new chapter in the chemistry of inorganic fluorides. A decrease of the sintering temperature of the powders with nanometer grains is very important for preparing dense fluoride ceramics of complicated compositions and other polycrystalline forms of fluoride materials. __________ Translated from Kristallografiya, Vol. 50, No. 3, 2005, pp. 524–531. Original Russian Text Copyright ? 2005 by Sobolev, Sviridov, Fadeeva, Sul’yanov, Sorokin, Zhmurova, Herrero, Landa-Canovas, Rojas.