Crystal structure and physical properties of the novel ternary intermetallics URuSi3−x and U3Ru2Si7

Two novel ternary intermediate phases, namely URuSi_3−x (x=0.11) and U₃Ru₂Si₇ were found in the Si-rich part of the U-Ru-Si phase diagram. Single crystal X-ray diffraction measurements, carried out at room temperature, indicated that URuSi_3−x crystallizes in its own tetragonal type structure (space group P4/nmm, no. 129; unit cell parameters: a=12.108(1) Å and c=9.810(1) Å), being a derivative of the BaNiSn₃-type structure. U₃Ru₂Si₇ adopts in turn a disordered orthorhombic La₃Co₂Sn₇-type structure (space group Cmmm, no. 65; unit cell parameters: a=4.063(1) Å, b=24.972(2) Å and c=4.072(1) Å). As revealed by magnetization, electrical resistivity and specific heat measurements, both compounds order magnetically at low temperatures. Namely URuSi_3−x is a ferromagnet with T_C=45 K, and U₃Ru₂Si₇ shows ferrimagnetic behavior below T_C=29 K.     

On the system cerium-platinum-silicon

Phase relations in the ternary system Ce-Pt-Si have been established for the isothermal section at 800 °C based on X-ray powder diffraction, metallography, scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) techniques on about 120 alloys, which were prepared by various methods employing arc-melting under argon or powder reaction sintering. Nineteen ternary compounds were observed. Atom order in the crystal structures of τ₁₈-Ce₅(Pt,Si)₄ (Pnma; a=0.77223(3) nm, b=1.53279(8) nm c=0.80054(5) nm), τ₃-Ce₂Pt₇Si₄ (Pnma; a=1.96335(8) nm, b=0.40361(4) nm, c=1.12240(6) nm) and τ₁₀-CePtSi₂ (Cmcm; a=0.42943(2) nm, b=1.67357(5) nm, c=0.42372(2) nm) was determined by direct methods from X-ray single-crystal CCD data and found to be isotypic with the Sm₅Ge₄-type, the Ce₂Pt₇Ge₄-type and the CeNiSi₂-type, respectively. Rietveld refinements established the atom arrangement in the structures of Pt₃Si (Pt₃Ge-type, C2/m, a=0.7724(2) nm, b=0.7767(2) nm, c=0.5390(2) nm, β=133.86(2)°), τ₁₆-Ce₃Pt₅Si (Ce₃Pd₅Si-type, Imma, a=0.74025(8) nm, b=1.2951(2) nm, c=0.7508(1) nm) and τ₁₇-Ce₃PtSi₃ (Ba₃Al₂Ge₂-type, Immm, a=0.41065(5) nm, b=0.43221(5) nm, c=1.8375(3) nm). Phase equilibria in Ce-Pt-Si are characterised by the absence of cerium solubility in platinum silicides. Cerium silicides and cerium platinides, however, dissolve significant amounts of the third component, whereby random substitution of the almost equally sized atom species platinum and silicon is reflected in extended homogeneous regions at constant Ce content such as for τ₁₃-Ce(Pt_xSi_1−x)₂, τ₆-Ce₂Pt_3+xSi_5−x or τ₇-CePt_2−xSi_2+x.     

Synthesis and crystal structure of RMgSi2 compounds (R=La, Ce, Pr, Nd), a particular example of linear intergrowth

A new series of rare earth compounds with stoichiometry RMgSi₂ (R=La, Ce, Pr, Nd) is reported. The single crystal X-ray diffraction showed that CeMgSi₂, which melts congruently at 1200 °C, crystallizes in a new tetragonal structure type (I4₁/amd, tI32, a=4.2652(4) Å, c=36.830(4) Å, Z=8; wR₂=0.042 (19 parameters, 393F₀²), R₁=0.018 (297F₀>4σF₀). The crystal structure of CeMgSi₂ can be formally built up by alternating along the z direction four CeMg₂Si₂-type CeMg₂Si₂ slabs with four AlB₂-type CeSi₂ slabs, one after the other. The structural model obtained from a CeMgSi₂ single crystal has been confirmed for the La, Pr and Nd homologous compounds by means of Rietveld refinement. The trend of the unit-cell parameters, plotted versus the R³⁺ ionic radius, shows a linear behaviour, which strongly suggests a trivalent state for the Ce atoms. An analysis of the features of this new structure is reported, in comparison with the other known CeMg₂Si₂/AlB₂-type linear intergrowth compounds.     

Ternary rare-earth bismuthides RE5SiBi2 and RE5GeBi2 (RE=La-Nd, Gd-Er): Stabilization of the β-Yb5Sb3-type structure through tetrel substitution

Ternary bismuthides RE₅TtBi₂ containing rare-earth (RE=La-Nd, Gd-Er) and tetrel (Tt=Si, Ge) atoms have been prepared by arc-melting of the elements followed by annealing at 800 °C. They adopt the β-Yb₅Sb₃-type structure (Pearson symbol oP32, space group Pnma, Z=4), as revealed through analysis by single-crystal X-ray diffraction on Ce₅Si_0.869(4)Bi_2.131(4) and powder X-ray diffraction on Ce₅GeBi₂. Cell parameters for the entire series lie in the ranges of a=12.8-11.8 Å, b=9.6-9.0 Å, and c=8.4-7.9 Å. Solid solubility in Ce₅Si_xBi_3−x and Pr₅Si_xBi_3−x (approximately 0.9≤x≤1.2, depending on the RE member) is much more limited compared to the antimonides, consistent with a highly ordered structure in which the two possible anion sites are essentially segregated into a smaller one occupied by Tt atoms (CN7) and a larger one occupied by Bi atoms (CN9). Band structure calculations on La₅SiBi₂ confirm the importance of La-La bonding interactions near the Fermi level. X-ray photoelectron spectra support the presence of partially anionic Bi atoms, as indicated by a small negative binding energy shift relative to elemental Bi. The Ce and Pr members undergo magnetic transitions at low temperatures, possibly involving ferromagnetic interactions, that are strongly influenced by the nature of the Tt atom.     

Physical and optical properties of the quaternary sulfides SrCu2MS4 and EuCu2MS4 (M=Ge and Sn)

Four quaternary sulfides SrCu₂MS₄ and EuCu₂MS₄ (M=Ge and Sn) were prepared from a thoroughly ground mixture of EuS or SrS, Cu, or Sn, and S in stoichiometric proportions. Electrical conductivity measurements on pressed pellets showed that all the phases are semiconductors. The optical band gaps were assessed at 2.8 eV for SrCu₂GeS₄, 2.1 eV for SrCu₂SnS₄, 2.2 eV for EuCu₂SnS₄, and 1.6 eV for EuCu₂GeS₄. Both Sr-based compounds present a temperature-independent paramagnetism, of about +135×10⁻⁶ and +92×10⁻⁶ emu/mol, for SrCu₂SnS₄ and SrCu₂GeS₄, respectively. In the case of the europium compounds, they follow a Curie-Weiss dependence above 1.8 K (EuCu₂GeS₄) and above 4 K (for EuCu₂SnS₄), with values of the magnetic effective moment μ_eff and the Curie-Weiss temperature Θ, equal to 6.27 μ_B and −2.8 K for EuCu₂GeS₄, and 6.81 μ_B and +0.7 K, for EuCu₂SnS₄. The experimental magnetic moments confirm that the europium ion is in divalent state, similar to Sr in the related compounds.     

Crystal structure and electronic properties of the new compounds U3Co12−xX4 with X=Si, Ge

The new compounds U₃Co_12−xX₄ with X=Si, Ge were prepared by direct solidification of the corresponding liquid phase, followed by subsequent annealing at 1173 K. Single crystal X-ray diffraction carried out at room temperature showed that they crystallize with the hexagonal space group P6₃/mmc (no.194) and the unit-cell parameters a=8.130(5), c=8.537(5) Å and a=8.256(1), c=8.608(1) Å for the silicide and germanide, respectively. Their crystal structure derives from the EuMg_5.2 structure type, and is closely related to the Sc₃Ni₁₁Si₄ and Gd₃Ru_4−xAl_12+x types. For the present compounds, no substitution mechanisms have been observed, the partial occupancy of one Co site results from the presence of vacancies, only. The homogeneity ranges, evaluated by energy dispersive spectroscopy analysis, extend from x=0.0(2) to 0.3(2) and from x=0.0(2) to 1.0(2) for U₃Co_12−xSi₄ and U₃Co_12−xGe₄, respectively. The electronic properties of both compounds were investigated by means of DC magnetic susceptibility and DC electrical resistivity measurements. The U₃Co_12−xX₄ compounds are both Pauli paramagnets with their electrical resistivity best described as poor metallic or dirty metallic behavior.     

The ternary system cerium-rhodium-silicon

Phase relations have been established in the ternary system Ce-Rh-Si for the isothermal section at 800 °C based on X-ray powder diffraction and EPMA on about 80 alloys, which were prepared by arc melting under argon or by powder reaction sintering. From the 25 ternary compounds observed at 800 °C 13 phases have been reported earlier. Based on XPD Rietveld refinements the crystal structures for 9 new ternary phases were assigned to known structure types. Structural chemistry of these compounds follows the characteristics already outlined for their prototype structures: τ₇—Ce₃RhSi₃, (Ba₃Al₂Ge₂-type), τ₈—Ce₂Rh_3−xSi_3+x (Ce₂Rh_1.35Ge_4.65-type), τ₁₀—Ce₃Rh_4−xSi_4+x (U₃Ni₄Si₄-type), τ₁₁—CeRh₆Si₄ (LiCo₆P₄-type), τ₁₃—Ce₆Rh₃₀Si_19.3 (U₆Co₃₀Si₁₉-type), τ₁₈—Ce₄Rh₄Si₃ (Sm₄Pd₄Si₃-type), τ₂₁—CeRh₂Si (CeIr₂Si-type), τ₂₂—Ce₂Rh_3+xSi_1−x (Y₂Rh₃Ge-type) and τ₂₄—Ce₈(Rh_1−xSi_x)₂₄Si (Ce₈Pd₂₄Sb-type). For τ₂₅—Ce₄(Rh_1−xSi_x)₁₂Si a novel bcc structure was proposed from Rietveld analysis. Detailed crystal structure data were derived for τ₃—CeRhSi₂ (CeNiSi₂-type) and τ₆—Ce₂Rh₃Si₅ (U₂Co₃Si₅-type) by X-ray single crystal experiments, confirming the structure types. The crystal structures of τ₄—Ce₂₂Rh₂₂Si₅₆, τ₅—Ce₂₀Rh₂₇Si₅₃ and τ₂₃—Ce_33.3Rh_58.2−55.2Si_8.5−11.5 are unknown. High temperature compounds with compositions Ce₁₀Rh₅₁Si₃₃ (U₁₀Co₅₁Si₃₃-type) and CeRhSi (LaIrSi-type) have been observed in as-cast alloys but these phases do not participate in the phase equilibria at 800 °C.     

Analysis of the electronic structure of Hf(Si0.5As0.5)As by X-ray photoelectron and photoemission spectroscopy

The ternary hafnium silicon arsenide, Hf(Si_xAs_1−x)As, has been synthesized with a phase width of 0.5?x?0.7. Single-crystal X-ray diffraction studies on Hf(Si_0.5As_0.5)As showed that it adopts the ZrSiS-type structure (Pearson symbol tP6, space group P4/nmm, Z=2, a=3.6410(5) Å, c=8.155(1) Å). Physical property measurements indicated that it is metallic and Pauli paramagnetic. The electronic structure of Hf(Si_0.5As_0.5)As was investigated by examining plate-shaped crystals with laboratory-based X-ray photoelectron spectroscopy (XPS) and synchrotron radiation photoemission spectroscopy (PES). The Si 2p and As 3d XPS binding energies were consistent with assignments of anionic Si¹⁻ and As^1-. However, the Hf charge could not be determined by analysis of the Hf 4f binding energy because of electron delocalization in the 5d band. To examine these charge assignments further, the valence band spectrum obtained by XPS and PES was interpreted with the aid of TB-LMTO band structure calculations. By collecting the PES spectra at different excitation energies to vary the photoionization cross-sections, the contributions from different elements to the valence band spectrum could be isolated. Fitting the XPS valence band spectrum to these elemental components resulted in charges that confirm that the formulation of the product is Hf²⁺[(Si_0.5As_0.5)As]²⁻.     

Quaternary selenostannates Na2−xGa2−xSn1+xSe6 and AGaSnSe4 (A=K, Rb, and Cs) through rapid cooling of melts. Kinetics versus thermodynamics in the polymorphism of AGaSnSe4

The quaternary alkali-metal gallium selenostannates, Na_2−xGa_2−xSn_1+xSe₆ and AGaSnSe₄ (A=K, Rb, and Cs), were synthesized by reacting alkali-metal selenide, Ga, Sn, and Se with a flame melting-rapid cooling method. Na_2−xGa_2−xSn_1+xSe₆ crystallizes in the non-centrosymmetric space group C2 with cell constants a=13.308(3) Å, b=7.594(2) Å, c=13.842(3) Å, β=118.730(4)°, V=1226.7(5) Å³. α-KGaSnSe₄ crystallizes in the tetragonal space group I4/mcm with a=8.186(5) Å and c=6.403(5) Å, V=429.1(5) Å³. β-KGaSnSe₄ crystallizes in the space group P2₁/c with cell constants a=7.490(2) Å, b=12.578(3) Å, c=18.306(5) Å, β=98.653(5)°, V=1705.0(8) Å³. The unit cell of isostructural RbGaSnSe₄ is a=7.567(2) Å, b=12.656(3) Å, c=18.277(4) Å, β=95.924(4)°, V=1741.1(7) Å³. CsGaSnSe₄ crystallizes in the orthorhombic space group Pmcn with a=7.679(2) Å, b=12.655(3) Å, c=18.278(5) Å, V=1776.1(8) Å³. The structure of Na_2−xGa_2−xSn_1+xSe₆ consists of a polar three-dimensional network of trimeric (Sn,Ga)₃Se₉ units with Na atoms located in tunnels. The AGaSnSe₄ possess layered structures. The compounds show nearly the same Raman spectral features, except for Na_2−xGa_2−xSn_1+xSe₆. Optical band gaps, determined from UV-Vis spectroscopy, range from 1.50 eV in Na_2−xGa_2−xSn_1+xSe₆ to 1.97 eV in CsGaSnSe₄. Cooling of the melts of KGaSnSe₄ and RbGaSnSe₄ produces only kinetically stable products. The thermodynamically stable product is accessible under extended annealing, which leads to the so-called γ-form (BaGa₂S₄-type) of these compounds.     

Phase stability and chemical composition dependence of the thermoelectric properties of the type-I clathrate Ba8AlxSi46−x (8≤x≤15)

Phase stability of the type-I clathrate compound Ba₈Al_xSi_46−x and the thermoelectric property dependence on chemical composition are presented. Polycrystalline samples were prepared by argon arc melting and annealing. Results of powder X-ray diffraction and electron microprobe analysis show that the type-I structure is formed without framework deficiency for 8≤x≤15. Lattice constant a increases linearly with the increase of x. Thermoelectric properties were measured for x=12, 14 and 15. The Seebeck coefficients are negative, with the absolute values increasing with x. The highest figure of merit zT=0.24 was observed for x=15 at T=1000 K, with carrier electron density n=3×10²¹ cm⁻³. A theoretical calculation based on the single parabolic band model reveals the optimum carrier concentration to be n∼4×10²⁰ cm⁻³, where zT∼0.7 at T=1000 K is predicted.     

Organosilicon hypersilylchalcogenolates and related compounds

Reaction of potassium hypersilylchalcogenolates (Me₃Si)₃SiEK (E = S, Se, Te) with organochlorosilanes R_4 − xSiCl_x (R = Me, Ph; x = 1-4) and methylchlorodisilanes (Si₂Me₅Cl, 1,2-Si₂Me₄Cl₂) yields organosilicon hypersilylchalcogenolates [(Me₃Si)₃SiE]_xSiR_4 − x (x = 1-4) and [(Me₃Si)₃SiE]_xSi₂Me_6 − x (x = 1, 2). A partial substitution product, [(Me₃Si)₃SiSe]₂SiPhCl (2) has been obtained by reaction of PhSiCl₃ with 1.5 equivalents (Me₃Si)₃SiSeK. Besides characterization by ¹H, ¹³C, ²⁹Si, ⁷⁷Se and ¹²⁵Te NMR spectroscopy the compounds [(Me₃Si)₃SiTe]₂SiPh₂ (1), [(Me₃Si)₃SiSe]₂SiPhCl (2) and [(Me₃Si)₃SiSe]₂Si₂Me₄(3) have also been analyzed by crystal structure analyses.Starting from (Me₃Si)₅Si₂K treatment with sulfur gave the highly branched potassium heptasilanylthiolate (Me₃Si)₅Si₂SK. Reactions with methylchlorosilanes Me_4 − xSiCl_x (x = 1, 2, 3) yielded organosilicon heptasilanylthiolates [(Me₃Si)₃Si-(Me₃Si)₂Si-S]_xSiMe_3 − x.     

Order-disorder transition and valence state of ytterbium in YbAuxGa2−x (0.26≤x≤1.31)

The intermetallic compounds YbAu_xGa_2−x (0.26≤x≤1.31) were synthesized by melting of elemental components and subsequent annealing. The crystal structure of YbAu_1.04Ga_0.96 was investigated using single-crystal X-ray diffraction data: structure type TiNiSi, space group Pnma, a=7.1167(3) Å, b=4.5019(3) Å, c=7.7083(3) Å, R_F=0.028 for 27 variables and 441 reflections. At 600 °C this compound is described as partially substituted TiNiSi type and shows a homogeneity range around the equiatomic composition YbAu_xGa_2−x (0.94≤x≤1.19). For the gallium- (0.26≤x≤0.83) and gold-rich (1.21≤x≤1.31) regions, the KHg₂ type of crystal structure (space group Imma) with mixed Au/Ga occupation is found. A temperature-driven phase transition for the composition YbAuGa from ordered TiNiSi to disordered KHg₂ structure type is observed at 629 °C. Yb L_III X-ray absorption spectra indicate an intermediate valence of +2.5 for Yb atoms in YbAuGa. For samples deviating from this composition a further reduced valence of Yb is observed. Magnetic susceptibility studies show a non-magnetic 4f¹⁴ ground state of Yb atoms with thermal fluctuations towards the 4f¹³ state.     

Electron-poor SrAuxIn4−x (0.5?x?1.2) and SrAuxSn4−x (1.3?x?2.2) phases with the BaAl4-type structure

Solid solutions SrAu_xIn_4−x (0.5?x?1.2) and SrAu_xSn_4−x (1.3?x?2.2) have been prepared at 700 °C and their structures characterized by powder and single-crystal X-ray diffraction. They adopt the tetragonal BaAl₄-type structure (space group I4/mmm, Z=2; SrAu_1.1(1)In_2.9(1), a=4.5841(2) Å, c=12.3725(5) Å; SrAu_1.4(1)Sn_2.6(1), a=4.6447(7) Å, c=11.403(2) Å), with Au atoms preferentially substituting into the apical over basal sites within the anionic network. The phase width inherent in these solid solutions implies that the BaAl₄-type structure can be stabilized over a range of valence electron counts (vec), 13.0-11.6 for SrAu_xIn_4−x and 14.1-11.4 for SrAu_xSn_4−x. They represent new examples of electron-poor BaAl₄-type compounds, which generally have a vec of 14. Band structure calculations confirm that substitution of Au, with its smaller size and fewer number of valence electrons, for In or Sn atoms enables the BaAl₄-type structure to be stabilized in the parent binaries SrIn₄ and SrSn₄, which adopt different structure types.     

Mn5Si3-type host-interstitial boron rare-earth metal silicide compounds RE5Si3: Crystal structures, physical properties and theoretical considerations

A series of binary rare-earth metal silicides RE₅Si₃ and ternary boron-interstitial phases RE₅Si₃B_x (RE=Gd, Dy, Ho, Lu, and Y) adopting the Mn₅Si₃-type structure, have been prepared from the elemental components by arc melting. Boron “stuffed” phases were subsequently heated at 1750 K within a high-frequency furnace. Crystal structures were determined for both binary and ternary series of compounds from single-crystal X-ray data: hexagonal symmetry, space group P6₃/mcm, Z=2. Boron insertion in the host binary silicides results in a very small decrease of the unit cell parameters with respect to those of the binaries. According to X-ray data, partial or nearly full boron occupancy of the interstitial octahedral sites in the range 0.6-1 is found. The magnetic properties of these compounds were characterized by the onset of magnetic ordering below 100 K. Boron insertion induces a modification of the transition temperature and θ_p values in most of the antiferromagnetic binary silicides, with the exception of the ternary phase Er₅Si₃B_x which was found to undergo a ferromagnetic transition at 14 K. The electrical resistivities for all binary silicides and ternary boron-interstitial phases resemble the temperature dependence of metals, with characteristic changes of slope in the resistivity curves due to the reduced electron scattering in the magnetically ordered states. Zintl-Klemm concept would predict a limiting composition RE₅Si₃B_0.6 for a valence compound and should then preclude the stoichiometric formula RE₅Si₃B. Density functional theory calculations carried out on some RE₅Si₃Z_x systems for different interstitial heteroatoms Z and different x contents from 0 to 1 give some support to this statement.     

Preparation, structure and photoluminescence properties of Eu and Ce-doped SrYSi4N7

Undoped and Eu²⁺ or Ce³⁺-doped SrYSi₄N₇ were synthesized by solid-state reaction method at 1400-1660 °C under nitrogen/hydrogen atmosphere. The crystal structure was refined from the X-ray powder diffraction data by the Rietveld method. SrYSi₄N₇ and EuYSi₄N₇, being isotypic with the family of compounds MYbSi₄N₇ (M=Sr, Eu, Ba) and BaYSi₄N_7, crystallize with the hexagonal symmetry: space group P6₃mc (No. 186), Z=2, a=6.0160 (1) Å, c=9.7894 (1) Å, V=306.83(3) Å³; and a=6.0123 (1) Å, c=9.7869 (1) Å, V=306.37(1) Å³, respectively. Photoluminescence properties have been studied for Sr_1−xEu_xYSi₄N₇ (x=0-1) and SrY_1−xCe_xSi₄N₇ (x=0-0.03) at room temperature. Eu²⁺-doped SrYSi₄N₇ shows a broad yellow emission band peaking around 548-570 nm, while Ce³⁺-doped SrYSi₄N₇ exhibits a blue emission band with a maximum at about 450 nm. SrYSi₄N₇:Eu²⁺ can be very well excited by 390 nm radiation, which makes this material attractive as conversion phosphor for LED lighting applications.     

Phase formation, crystal structures and magnetic properties of perovskite-type phases in the system La2Co1+z(MgxTi1−x)1−zO6

Perovskite-type cobaltates in the system La₂Co_1+z(Mg_xTi_1−x)_1−zO₆ were studied for z=0≤x≤0.6 and 0≤x<0.9, using X-ray and neutron powder diffraction, electron diffraction (ED), magnetic susceptibility measurements and X-ray absorption near-edge structure (XANES) spectroscopy. The samples were synthesised using the citrate route in air at 1350 °C. The space group symmetry of the structure changes from P2₁/n via Pbnm to R3¯c with both increasing Mg content and increasing Co content. The La₂Co(Mg_xTi_1−x)O₆ (z=0) compounds show anti-ferromagnetic couplings of the magnetic moments for the Co below 15 K for x=0, 0.1 and 0.2. XANES spectra show for the compositions 0≤x≤0.5 a linear decrease in the L₃/(L₃+L₂) Co-L_2,3 edge branching ratio with x, in agreement with a decrease of the average Co ion spin-state, from a high-spin to a lower-spin-state, with decreasing nominal Co²⁺ ion content.     

Magnetostructural correlations in the antiferromagnetic Co2−x Cux(OH)AsO4 (x=0 and 0.3) phases

The Co_2−xCu_x(OH)AsO₄ (x=0 and 0.3) compounds have been synthesized under mild hydrothermal conditions and characterized by X-ray single-crystal diffraction and spectroscopic data. The hydroxi-arsenate phases crystallize in the Pnnm orthorhombic space group with Z=4 and the unit-cell parameters are a=8.277(2) Å, b=8.559(2) Å, c=6.039(1) Å and a=8.316(1) Å, b=8.523(2) Å, c=6.047(1) Å for x=0 and 0.3, respectively. The crystal structure consists of a three-dimensional framework in which M(1)O₅-trigonal bipyramid dimers and M(2)O₆-octahedral chains (M=Co and Cu) are present. Co₂(OH)AsO₄ shows an anomalous three-dimensional antiferromagnetic ordering influenced by the magnetic field below 21 K within the presence of a ferromagnetic component below the ordering temperature. When Co²⁺ is partially substituted by Cu²⁺ions, Co_1.7Cu_0.3(OH)AsO₄, the ferromagnetic component observed in Co₂(OH)AsO₄ disappears and the antiferromagnetic order is maintained in the entire temperature range. Heat capacity measurements show an unusual magnetic field dependence of the antiferromagnetic transitions. This λ-type anomaly associated to the three-dimensional antiferromagnetic ordering grows with the magnetic field and becomes better defined as observed in the non-substituted phase. These results are attributed to the presence of the unpaired electron in the dx²−y² orbital and the absence of overlap between neighbour ions.     

Crystal structure and magnetic properties of the UFe7Al5 uranium-iron aluminide

The ternary compound UFe₇Al₅ was synthesized by arc melting, followed by annealing at 850°C. The crystal structure was determined by single-crystal X-ray diffraction and refined to a residual value of R=0.039 (S=1.030), with lattice parameters a=8.581(2) Å and c=4.946(1) Å. This compound is a new extreme composition in the family of intermetallics with general formula UFe_xAl_12−x crystallizing in the tetragonal ThMn₁₂-type structure, space group I4/mmm. In contrast to UFe_xAl_12−x within the composition range 4?x?6, in UFe₇Al₅ the additional iron atom is found in the 8i equipositions. Magnetization measurements versus temperature show two magnetic transitions at 363 and 275 K, respectively, with a ferromagnetic behavior below the highest temperature transition. ⁵⁷Fe Mössbauer data indicate that the high-temperature transition is related to the ordering of the iron atoms. The dependence of the isomer shifts and magnetic hyperfine fields on the crystallographic site and on the number of the iron nearest neighbors is similar to that observed in the other UFe_xAl_12−x and rare-earth analogues. The magnetic hyperfine field values of iron atoms on 8i sites is larger than in the other sites, in agreement with previous data obtained for other ThMn₁₂-type compounds.     

Structure and photoluminescence properties of Ce-doped novel silicon-oxynitride Ba4−zMzSi8O20−3xN2x (M=Mg, Ca, Sr)

Structural and photoluminescence properties of undoped and Ce³⁺-doped novel silicon-oxynitride phosphors of Ba_4−zM_zSi₈O_20−3xN_2x (M=Mg, Sr, Ca) are reported. Single-phase solid solutions of Ba_4−zM_zSi₈O_20−3xN_2x oxynitride were synthesized by partial substitutions of 3O²⁻→2N³⁻ and Ba→M (M=Mg, Ca, Sr) in orthorhombic Ba₂Si₄O₁₀. The influences of the type of alkaline earth ions of M, the Ce³⁺ concentration on the photoluminescence properties and thermal quenching behaviors of Ba₃MSi₈O_20−3xN_2x (M=Mg, Ca, Sr, x=0.5) were investigated. Under excitation at about 330 nm, Ba₃MSi₈O_20−3xN_2x:Ce³⁺ (x=0.5) exhibits efficient blue emission centered at 400-450 nm in the range of 350-650 nm owing to the 5d→4f transition of Ce³⁺. The emission band of Ce³⁺ shifts to long wavelength by increasing the ionic size of M due to the modification of the crystal field, as well as the Ce³⁺ concentrations due to the Stokes shift and energy transfer or reabsorption of Ce³⁺ ions. Among the silicon-oxynitride phosphors of Ba₃MSi₈O_18.5N:Ce³⁺, M=Sr_0.6Ca_0.4 possesses the best thermal stability probably related to its high onset of the absorption edge of Ce³⁺.     

Structure and physical properties of ternary W5Si3-type antimonides and bismuthides Zr5M1-xPn2+x (M=Cr, Mn; Pn=Sb, Bi)

Four new ternary compounds Zr₅M_1-xPn_2+x (M=Cr, Mn; Pn=Sb, Bi) were synthesized by arc-melting and annealing at 800 °C. They crystallize in the tetragonal W₅Si₃-type structure. The crystal structure of Zr₅Cr_0.49(2)Sb_2.51(2) was refined from powder X-ray diffraction data by the Rietveld method (Pearson symbol tI32, tetragonal, space group I4/mcm, Z=4, a=11.1027(6) Å, c=5.5600(3) Å). Four-probe electrical resistivity measurements on sintered polycrystalline samples indicated metallic behavior. Magnetic susceptibility measurements between 2 and 300 K revealed temperature-independent Pauli paramagnetism for Zr₅Cr_1-xSb_2+x and Zr₅Cr_1-xBi_2+x, but a strong temperature dependence for Zr₅Mn_1-xSb_2+x and Zr₅Mn_1-xBi_2+x which was fit to the Curie-Weiss law for the latter with θ=-11.3 K and μ_eff=1.81(1) μ_B. Band structure calculations for Zr₅Cr_0.5Sb_2.5 support a structural model in which Cr and Sb atoms alternate within the chain of interstitial sites formed at the centers of square antiprismatic Zr₈ clusters.