TEM Investigation of Dislocations in RNi2B2C (R = Y,Tb, Ho,Er, Y0.6Tb0.4, Er0.8Tb0.2)

To evaluate the influence of different rare earth metals on dislocation type and stacking fault occurrence in RNi2B2C compounds samples with R = Y, Tb, Ho, Er, Y_0.6Tb_0.4 and Er_0.8Tb_0.2 were investigated. As a result of the TEM analysis the parameter decisive for the lattice defects in these compounds is not the type of components but the annealing treatment of the samples. In well homogenized material the dominant Burgers vector of perfect dislocations was <100] and stacking faults are hardly found. In inhomogeneous samples the dominant Burgers vector was <110] and the perfect dislocations often lie in the planes of the numerous stacking faults. In both types of materials the experimental results hint at the existence of two different slip systems.     

Synthesis and Luminescence Characteristics of LiMgAlF6:Ln3+ (Ln = Ce,Eu, Tb)

By solid state reaction, LiMgAlF₆ and LiMgAlF₆: Ln³⁺ are synthetized with the ratio 120/100/110 of LiF/MgF₂/AlF₃, at 1008 K, in high-purity Ar stream. Their crystal structure which belongs to hexagonal system are determined by X-Ray-Diffraction (XRD). Luminescence characteristics of Ce³⁺, Eu³⁺, Tb³⁺ and sensitization of Ce³⁺ to Tb³⁺ in LiMgAlF₆ are studied. It is shown that the sensitization of Ce³⁺ to Tb³⁺ is efficient and a bright green emission is observed.     

Growth and characterization of Ca9 Ln(VO4)7 crystals (Ln = Y, La, or Gd)

Ca₉ Ln(VO₄)₇ single crystals (Ln = Y, La, or Gd) have been grown by the Czochralski method. The grown crystals deviate from the stoichiometric ratio Ca/Ln; this deviation increases in the series from Y to Gd.     

Microstructure of eutectic composites Ln 1?x Ln′ x MnO3 (Ln = Eu or Tb; Ln′ = Y or Ho) near the transition between the orthorhombic structure and hexagonal structures

Multiferroic crystals Ln _{1 ? x} MnO₃ (Ln = Eu or Tb; Ln?? = Y or Ho) have been grown by floating-zone melting; the compositions of these crystals are close to the point of concentration transition from the orthorhombic structure to the hexagonal phase. Scanning microscopy has revealed that the crystal boules have a regular lamellar structure in the form of alternating layers of the orthorhombic and hexagonal phases; this structure is typical of the materials obtained by the directional solidification of eutectic composites. The local chemical and phase compositions and the unit-cell parameters of the phases have been determined. The microstructure and morphology of the lamellar structures are described for different growth conditions. The mutual orientation of the crystallographic axes of the orthorhombic and hexagonal phases in the neighboring layers has been determined by electron backscatter diffraction. The orientational features are considered from the point of view of the crystal structure of both phases.     

CF4气氛中生长Re: LiM(Re=Tm,Ce;M=Lu,Y)F4晶体

本文在CF4气氛中以提拉法成功地生长出高质量的掺入Tm3+、Ce3+的LiLuF4和LiYF4晶体,对比了Ar和CF4气氛中生长的LiYF4晶体的红外光谱特性,讨论了CF4气氛对LiM(M=Y,Lu)F4晶体生长的影响.同时测试了Tm3+、Ce3+在LiLuF4和LiYF4晶体中的有效分凝系数,从离子半径和晶胞畸变的角度,讨论了Tm3+、Ce3+在LiLuF4和LiYF4晶体中有效分凝系数差别的产生原因.     

Hydrothermal synthesis of [Mn(HTPO)(BIPY)] (H3TPO = tris-(4-carboxylphenyl)phosphine oxide): a crosslinked coordination polymer

The hydrothermal synthesis and crystal structure of the title compound is reported. The structure consists of 1-D looped chains with the HTPO ligand binding through the phosphoryl and two carboxylate oxygens to manganese atoms. The carboxylic acid group is hydrogen bonded to adjacent chains forming a 2-D hydrogen bonded network. The crystals are triclinic and the space group isP-1 with a = 11.6767(8) Å, b = 10.8680(8) Å and c = 11.4232(87rpar; Å = 92.301(2)°, = 106.932(2)° and = 103.2390(10)° V = 1341.02(16) ų; Z = 2.     

Hydrothermal synthesis and characterization of micro/nanostructured ZnSn(OH)6/ZnO composite architectures

Micro/nanostructured ZnSn(OH)₆/ZnO composite architectures were synthesized through a simple one‐step hydrothermal method. Phase structure and morphology of the products were characterized by using X‐ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). ZnSn(OH)₆ microcubes and ZnO nanorods with uniform size were interconnected to form the micro/nanostructured architectures. ZnO nanorods preferentially grow at edges and corners of the microcubes. Morphology of the products was susceptible to concentration of the reactants. With increasing reactant concentration, the ZnO nanorods grown on the surfaces of ZnSn(OH)₆ microcubes disappeared. Meanwhile, the smooth surfaces of the ZnSn(OH)₆ microcubes become coarsened and were etched to spherical outlines. Growth mechanism of the micro/nanostructured ZnSn(OH)₆/ZnO composite architectures was discussed and thermal decomposition properties of the micro/nanostructured ZnSn(OH)₆/ZnO composite architectures at high temperature were examined. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Er,Yb:KGd(WO4)2激光晶体的生长

采用顶部籽晶熔盐法,以K2WO4为助熔剂生长出铒、镱共掺钨酸钆钾[Er,Yb：KGd（WO4）2简称Er,Yb：KGW]激光晶体。XRD分析结果表明晶体为低温相Er,Yb：KGW晶体,即β-Er,Yb：KGW晶体。通过差热分析测量,确定其相变温度和熔点分别为1020℃和1080℃。测量了晶体190-2000nm的室温透过光谱,结果表明除980nm的吸收谱带是Er^3＋离子和Yb^3＋离子的共同谱带之外,其余均属于Er^3＋离子。     

Crystal structure of double vanadates Ca9 R(VO4)7. II. R = Tb, Dy, Ho, and Y

Crystal structures of the compounds Ca₉ R(VO₄)₇ (R = Tb (I), Dy (II), Ho (III), and Y (IV) have been studied by the method of the full-profile analysis. All the compounds are crystallized in the trigonal system (sp. gr. R 3 c, Z = 6) with the unit-cell parameters (I) a = 10.8592(1), c = 38.035(1), V = 3884.2(2) ų; (II) a = 10.8564(1), c = 38.009(1) Å, V = 3879.6(2) ų, (III) a = 10.8565(1) and c = 37.995(1) Å, V = 3878.3(2) ų, and (IV) a = 10.8588(1), c = 37.995(1) Å, V = 3879.9(2) ų. In structures I–IV, rare earth and calcium cations occupy three positions—M(1), M(2), and M(5). Rare earth cations occupy the R ³⁺ positions almost in the same way: 2.7–2.6(2) cations in the M(1) position; 2.7–2.3(2) cations in the M(2) position, and 0.6–1.0(1) cation in the M(5) position. At the same time, the occupancy of the M(5) position regularly increases with a decrease of the R ³⁺ radius.     

New family of LnBaMn2O6 − γ manganites (Ln = Nd, Sm, and Gd)

A new family of manganites, LnBaMn₂O_{6 ? γ}(Ln = Nd, Sm, and Gd), is obtained by the method of topotactic reactions. In these compounds, rare-earth and barium ions are ordered, which results in a dramatic increase in the temperature of transition to the paramagnetic state. Thus, a SmBaMn₂O₆ compound with a disordered arrangement of Sm and Ba ions is a spin glass with the freezing temperature of magnetic moments T _f = 40 K, whereas in the state with an ordered Sm and Ba arrangement, the Curie temperature T _C, is ～ 280 K. Below T _C, a maximum in resistivity and magnetoresistance is observed. The possible models of magnetic ordering are discussed.     

Hydrothermal synthesis and characterization of (N(C2H5)4)4[VMo12V2O44]

The hydrothermal reaction of a mixture of Na₂MoO₄·2H₂O, V₂O₅, pyromellitic acid (1,2,4,5‐C₆H₂(COOH)₄), (C₂H₅)₄NCl and 0,1 M H₂SO₄ for 88 h at 180°C gives blue needle‐like crystals of [V^IV₂O₂(H₂O)₂ (C₆H₂(COO)₄)] in 20% yield (based on V) and dark blue prismatic crystals of the title compound, mixed‐valance (N(C₂H₅)₄)₄[VMo₁₂V₂O₄₄], 1, in 12% yield (based on Mo). 1 was investigated by means of elemental analysis, thermogravimetry, Fourier Transform Infrared Spectroscopy and Single Crystal X‐ray Diffraction Methods. Crystal data for the compound: monoclinic space group P2₁/c (No:14), a=13.7815(12) b=13.0271(9) c= 21.189(2) Å, β= 113.909(7)°, Z=2. Although [XM₁₄O₄₂]^‐n (X=P, Si, Ge, V and M=Mo and/or V) cores have been previously determined, this is the first time that [VMo₁₂V₂O₄₄]^‐4 core is synthesized and characterized. The structural difference between 1 and these HPOMs is the coordinational geometry of the central metal atoms. The central vanadium in 1 has an octahedral coordination geometry, whereas in literature, the central V, P, Si and Ge atoms in [V₁₅O₄₂]^‐9 / [SiM₈V₆O₄₂]^‐4 / [PM₈V₆O₄₂]^‐5 / [GeM₈V₆O₄₂]^‐4 have tetrahedral coordinational geometry. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of MAgSe4 (M=Rb, Cs)

Syntheses of the title compounds were achieved from supercritical amines. The single crystal X-ray characterization of both MAgSe₄ (M=Rb, Cs) members indicates that they are isostructural. The structure is built from five membered AgSe₄ rings that are stitched together through tetrahedrally coordinated Ag(I) ions to form one dimensional chains running parallel to the a-axis. These chains are separated from each other by the alkali metal cations. Crystal data: orthorhombic, P2₁2₁2₁, Z = 4. RbAgSe₄: a = 5.809(2), b = 8.927(3), c = 13.435(4) Å, U = 698.2(4) ų, and D _c = 4.851 g/cm³. CsAgSe₄: a = 5.855(2), b = 9.090(3), c = 13.885(4) Å, U = 739.0(4) ų, and D _c = 5.003 g/cm³. The anionic chain found in the title compounds has been observed previously, and comparisons among these phases show that the silver ion coordination in the chain varies as a function of cation size. Both the title compounds are valence precise and optical diffuse reflectance studies show that they are semiconductors with moderately large band gaps.     

Synthesis and structural characterization of dihexamethylenetetraminetetraaquocobalt(II) hexaaquocobalt(II) sulfate hexahydrate

The synthesis and crystal structure of a new three dimensional cobalt(II) complex [Co(C₆H₁₂N₄)₂(H₂O)₄Co(H₂O)₆][SO₄]₂.6H₂O are reported. It crystallizes in the triclinic space group P-1 with a = 13.394(3), b = 16.077(3), c = 9.282(2) Å, = 89.71(2), = 90.42(2), = 114.02(2)°, V = 1825.6(7)ų and Z = 2. The structure is comprised of [Co(C₆H₁₂N₄)₂ (H₂O)₄Co(H₂O)₆][SO₄]₂ units and H₂O molecules. Two molecules of ligand and four molecules of water chelate one type of Co^II in an octahedral fashion through two N and four O atoms: the four O atoms form the equatorial plane and the two N atoms occupy the apical positions. The other type of Co^II cation is chelated by six water molecules.     

CaB_8O_(11)(OH)_4晶体的水热生长、表征与非线性光学效应研究

本文研究了含水硼酸盐非线性光学晶体CaB_8O_(11)(OH)_4的生长方法及其基本性质.以H_3BO_3和CaO为原料,采用水热法在280～350 ℃生长了二水八硼酸钙(CaB_8O_(11)(OH)_4),并对其进行了XRD、TG-DSC、FT-IR、SHG、透过光谱测试;从结构上分析了其产生较大非线性光学效应的原因,其粉末倍频效应相当于同等粒度KDP的1～2倍,透过率在350～750 nm达到80;.     

Effect of Ca on HoPO4·nH2O (n = 1 and 2) crystallization from phosphoric acid solution

Ca‐substituted holmium phosphate, isomorphic with tetragonal form of HoPO₄·H₂O was synthesized by crystallization from boiling phosphoric acid (2 M H₃PO₄) solution containing 0.02M of Ho and 0–0.2 M of Ca. Calcium concentration, higher than 0.2 M Ca in solution resulted in biphasic solid crystallization: tetragonal HoPO₄·H₂O and orthorhombic HoPO₄·2H₂O. Ca incorporation in the solid according to substitution mechanism: Ca²⁺ + H⁺ ↔ Ho³⁺ was limited to ∼3 wt.% and was coupled with simultaneous incorporation of HPO₄²⁻. Ca for Ho substitution caused an expansion of the tetragonal unit cell of HoPO₄·H₂O, resulted from differences in the ionic radii (r_Ca > r_Ho). Effects of thermal treatment at 900 °C were as follows: (i) the orthorhombic admixture of HoPO₄·2H₂O re‐crystallized into tetragonal anhydrous HoPO₄, (ii) Ca–at first dissolved in crystal structure of HoPO₄·H₂O was expelled from it during re‐crystallization to form Ca(PO₃)₂, and that was associated with a contraction of the unit cell; a ‐ and c‐ axes went down to the level of Ca‐free anhydrous tetragonal form of HoPO₄. (iii) HPO₄²⁻ present in the solids as prepared underwent condensation according to reaction 2HPO₄²⁻ → P₂O₇⁴⁻ + H₂O. Scanning electron micrographs revealed significant changes in size and morphology of the crystals ranging from spherical globules of HoPO₄·H₂O formed in Ca‐free H₃PO₄ with increasing diameter in the presence of lower Ca concentration to rod‐like crystals organized in bundles resembling the “scheaf of wheat”, while crystallized from phosphoric acid solution with higher than 0.2 M Ca.     

Optical properties of trigonal single crystals (Yb,Tm)Al3(BO3)4 grown from fluxes based on the bismuth and lithium molybdates

The conditions for synthesis of Yb _x Tm_{1 − x} Al₃(BO₃)₄ (x = 0, 0.1, 0.2, 1.0) single crystals from fluxes based on bismuth trimolybdate Bi₂Mo₃O₁₂ and lithium molybdate Li₂MoO₄ are investigated. It is proposed to grow them by the group method on seeds. The polarized optical absorption spectra are measured for two mutually orthogonal linear polarizations at temperatures of 100 and 300 K.     

Synthesis,characterization, and structure of lanthanide picrate complexes with tetramethylenesulfoxide (TMSO)

A series of complexes with composition M(pic)₃(TMSO)₃ (M=La, Nd, Sm, Eu, Gd, Er, Yb, and Y) were synthesized and characterized. The electronic absorption spectrum of the Nd complex and the emission spectrum of the Eu complex were recorded and assigned. The unique compound, Sm(pic)₃(TMSO)_2.5(EtOH)_0.5, obtained by recrystallizatiori of Sm(pic)₃(TMSO)₃ from ethanol, was characterized by single-crystal X-ray analysis. The complex crystallizes in a monoclinic cell space groupP2₁/n witha=21.809(4)Å,b=15.811(3)Å,c=12.800(3)Å and =99.87(4)°. The coordination polyhedron about the Sm center is a tricapped trigonal prism involving the three picrates, which act as bidentate ligands via the phenoxo oxygen and an oxygen of an adjacent nitro group, as well as the oxygens of two TMSO ligands. The ninth position is statistically (50%) occupied by an oxygen atom of a third TMSO ligand and an oxygen atom of an ethanol molecule.     

Synthesis and luminescent properties of novel RENbO4:Ln3+ (RE = Y, Gd, Lu; Ln = Eu, Tb) micro-crystalline phosphors

Using rare earth coordination polymers with aromatic carboxylic acids as the precursors of rare earth oxide components, with polyethylene glycol (PEG) as the dispersing media, micro-crystalline phosphors RENbO₄:Ln³⁺ (RE = Y, Gd, Lu; Ln = Eu, Tb) have been synthesized by an in situ co-precipitation method. Both X-ray diffraction and scanning electron microscopy have shown that the resultant samples present are crystalline with ‘rice glue ball’ micro-morphology and crystalline grain sizes in the range of 1–2 μm. The luminescent properties of these phosphors have been studied, which show that the best photoluminescent performance is achieved for GdNbO₄:Tb³⁺ or Eu³⁺. This was because Gd³⁺ plays an important role to enhance the luminescence of Tb³⁺ or Eu³⁺ in an energy transfer process. In addition, the influence of the doping concentration on the fluorescence behaviors has been examined. With increase of the doping concentration from 1 mol% to 5 mol%, both the red emission intensity of Eu³⁺ and the green emission intensity of Tb³⁺ increase.     

Search for compounds of the NaBaR(BO3)2 family (R = La, Nd, Gd, and Yb) and the new NaBaYb(BO3)2 orthoborate

A search for compounds of the NaBaR(BO₃)₂ composition (where R = La³⁺, Nd³⁺, Gd³⁺, or Yb³⁺) is performed by solid state synthesis and spontaneous crystallization. A new compound, NaBaYb(BO₃)₂, is found in this series. It crystallizes in space group $R\bar 3$ and belongs to the family of sublayer complex orthoborates with isolated BO₃ groups NaBaR(BO₃)₂ (R = Y, Sc, and Yb). Theoretical X-ray powder diffraction patterns of NaBaY(BO₃)₂, NaBaSc(BO₃)₂, and NaBaYb(BO₃)₂ are calculated based on single-crystal data.     

Growth and characterization of ferroelectric‐ferroelastic Tb2(MoO4)3 crystals

Transparent and nearly colorless ferroelectric‐ferroelastic β′‐Tb₂(MoO₄)₃ (TMO) single crystals have been grown by the Czochralski (CZ) method. The single crystal structure was investigated by X‐ray powder diffraction and was shown to be a single phase with the structure similar as the β′‐Gd₂(MoO₄)₃ crystal. The optical transparency of the TMO crystal has been measured and the crystal is almost transparent in the visible and near infrared regions. The defects of TMO crystal were evaluated by etching technique and the ferroelectric domain structures were observed by an optical microscope. A high‐resolution X‐ray diffraction analysis demonstrates that the as‐grown TMO crystal possesses relatively high optical quality. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)