Crystal structures and magnetic properties of iron (III)-based phosphates: Na4NiFe(PO4)3 and Na2Ni2Fe(PO4)3

Crystal structures from two new phosphates Na₄NiFe(PO₄)₃ (I) and Na₂Ni₂Fe(PO₄)₃ (II) have been determined by single crystal X-ray diffraction analysis. Compound (I) crystallizes in a rhombohedral system (S. G: R-3c, Z = 6, a = 8.7350(9) Å, c = 21.643(4) Å, R₁ = 0.041, wR₂=0.120). Compound (II) crystallizes in a monoclinic system (S. G: C2/c, Z = 4, a = 11.729(7) Å, b = 12.433(5) Å, c = 6.431(2) Å, β = 113.66(4)°, R₁ = 0.043, wR₂=0.111). The three-dimensional structure of (I) is closely related to the Nasicon structural type, consisting of corner sharing [(Ni/Fe)O₆] octahedra and [PO₄] tetrahedra forming [NiFe(PO₄)₃]⁴⁺ units which align in chains along the c-axis. The Na⁺ cations fill up trigonal antiprismatic sites within these chains. The crystal structure of (II) belongs to the alluaudite type. Its open framework results from [Ni₂O₁₀] units of edge-sharing [NiO₆] octahedra, which alternate with [FeO₆] octahedra that form infinite chains. Coordination of these chains yields two distinct tunnels in which site Na⁺.The magnetization data of compound (I) reveal antiferromagnetic (AFM) interactions by the onset of deviations from a Curie-Weiss behaviour at low temperature as confirmed by Mössbauer measurements performed at 4.2 K. The corresponding temperature dependence of the reciprocal susceptibility χ⁻¹ follows a typical Curie-Weiss behaviour for T > 105 K. A canted AFM state is proposed for compound (II) below 46 K with a field-induced magnetic transition at H ≈ 19 kOe, revealed in the hysteresis loop measured at 5 K. This transition is most probably associated with a spin-flop transition.     

Microwave synthesis, structure, and magnetic properties of quasi-one-dimensional complex oxide Sr4LiMn2O9

The complex oxide Sr₄LiMn₂O₉ belonging to the A_3n+3mA′_nMn_3m+nO_9m+6n family (m = 3, n = 1) was prepared from a mixture of SrCO₃ and LiMn₂O₄ in a microwave furnace by the solid state reaction. The results of structural refinements and magnetic properties are presented. The crystal structure of Sr₄LiMn₂O₉ was solved using simultaneously X-ray and neutron diffraction data with the GSAS program in the space group P321 with unit cell parameters: a = 9.5721(7) Å, c = 7.8264(5) Å, V = 621.025 Å³, Z = 3. Sr₄LiMn₂O₉ was found to contain 2 independent 1D chains of face-shared polyhedrons with a sequence of two octahedrons and one trigonal prism. The chains are separated by strontium cations. The refinement results show that the octahedrons and trigonal prisms in the first chain orderly contain Mn and Li, respectively, whereas the second chain is characterized by mixed occupation of these structural positions. The temperature dependence of the magnetic susceptibility of Sr₄LiMn₂O₉ was found to be due to antiferromagnetically coupled dimers from magnetic Mn cations.     

Study on the crystal structure of the rare earth oxyborate Yb26B12O57 from powder X-ray and neutron diffraction

Yb₂₆B₁₂O₅₇, a rare earth oxyborate previously assigned as Yb₃BO₆, has been studied by various techniques including neutron and X-ray diffraction, ¹¹B NMR spectroscopy, electron diffraction and high angle angular dark field-scanning transmission electron microscopy (HADDF-STEM). It crystallizes in the space group C2/m with cell parameters of a = 24.5780(4) Å, b = 3.58372(5) Å, c = 14.3128(3) Å and β = 115.079(1)°. The structure consists of slabs of rare earth sesquioxide and borate groups. The sesquioxide part is identified from the structural refinement, and is observed from HADDF-STEM image, while elucidation of borate groups is not straightforward. An additional oxygen atom (O31), which links two B₂O₅ groups into a B₄O₁₁ polyanion, is identified from the analysis of neutron diffraction data. The occupancy of this oxygen site is only quarter, which results in a random distribution of B₄O₁₁ and B₂O₅ groups along the b-direction. The chemical formula of ytterbium oxyborate is Yb₂₆(BO₃)₄(B₂O₅)₂(B₄O₁₁)O_24, instead of the simple stoichiometric formula Yb₃BO₆. This compound is paramagnetic but its susceptibility deviated from the Curie-Weiss law at low temperature.     

Structure and electrical conduction behavior of LiZnVO4 ceramic prepared by solution-based chemical route

In the present work, an evaluation of the structural and electrical properties of a compound (LiZnVO₄) has been undertaken. This compound was prepared by solution-based chemical route. The electrical properties were measured using a.c. impedance spectroscopy method in the frequency range of 10³-10⁶ Hz at various temperatures from 28 to 300 °C. X-ray diffraction study indicates a rhombohedral unit cell structure with lattice parameters a = 14.1934 Å, b = 14.1934 Å, c = 9.4926 Å, V = 1656.12 (Å)³, α = 90°, β = 90° and γ = 120°. A field emission scanning electron micrograph reveals a polycrystalline texture of the compound with grains of unequal sizes ∼0.2-2.0 μm. The electrical conduction in the material is a thermally activated process due to the bulk effect. Frequency dependence of a.c. conductivity obeys Jonscher's universal law (σ_ac = σ_dc + Aωⁿ).     

Interstitial solid solution Hf5GaxSn3 (x = 0-1)

Formation of an interstitial solid solution Hf₅Ga_xSn₃ (x = 0-1) based on the binary compound Hf₅Sn₃ (structure type Mn₅Si₃, Pearson symbol hP16, space group P6₃/mcm, a = 8.36562(6), c = 5.70775(4) Å from X-ray powder diffraction) was established at 600 °C. The crystal structure (structure type Hf₅CuSn₃, ordered derivative of Ti₅Ga₄, hP18, P6₃/mcm) was refined on X-ray single-crystal diffraction data for three compositions: Hf₅Ga_0.16(3)Sn₃ (a = 8.3288(12), c = 5.6988(11) Å), Hf₅Ga_0.53(2)Sn₃ (a = 8.4205(12), c = 5.7655(12) Å) and Hf₅GaSn₃ (a = 8.5564(12), c = 5.7859(12) Å). The Ga atoms occupy Wyckoff position 2b at the centres of Hf₆ octahedral interstices.     

Dielectric and microwave properties of ZrO2 doped CaO-SiO2-B2O3 ceramic matrix composites

The behavior of dielectric and microwave properties against sintering temperature has been carried out on CaO-SiO₂-B₂O₃ ceramic matrix composites with ZrO₂ addition. The results indicated that ZrO₂ addition was advantageous to improve the dielectric and microwave properties. X-ray diffraction (XRD) patterns show that the major crystalline β-CaSiO₃ and a little SiO₂ phase existed at the temperature ranging from 950 °C to 1050 °C. At 0.5 wt% ZrO₂, CaO-SiO₂-B₂O₃ ceramic matrix composites sintered at 1000 °C possess good dielectric properties: ?_r = 5.85, tan δ = 1.59 × 10⁻⁴ (1 MHz) and excellent microwave properties: ?_r = 5.52, Q · f = 28,487 GHz (11.11 GHz). The permittivity of Zr-doped CaO-SiO₂-B₂O₃ ceramic matrix composites exhibited very little temperature dependence, which was less than ±2% over the temperature range of −50 to 150 °C. Moreover, the ZrO₂-doped CaO-SiO₂-B₂O₃ ceramic matrix composites have low permittivity below 5.5 over a wide frequency range from 20 Hz to 1 MHz.     

Ferroelectric relaxor behavior and dielectric spectroscopic study of 0.99(Bi0.5Na0.5TiO3)-0.01(SrNb2O6) solid solution

0.99(Bi_0.5Na_0.5TiO₃)-0.01(SrNb₂O₆) was prepared by simple solid state reaction route. Material stabilized in rhombohedral perovskite phase with lattice constants a = 3.9060 Å, α = 89.86° and a_h = 5.4852 Å, c_h = 6.7335 Å for hexagonal unit cells. Density of material was found 5.52 g_m/cm³ (92.9% of theoretical one) in the sample sintered at 950 °C. The temperature dependent dielectric constant exhibits a broad peak at 538 K (?_m = 2270) at 1 kHz that shows frequency dependent shifts toward higher temperature - typical relaxor behavior. Modified Curie-Weiss law was used to fit the dielectric data that exhibits almost complete diffuse phase transition characteristics. The dielectric relaxation obeys the Vogel-Fulcher relationship with the freezing temperature 412.4 K. Significant dielectric dispersion is observed in low frequency regime in both components of dielectric response and a small dielectric relaxation peak is observed. Cole-Cole plots indicate polydispersive nature of the dielectric relaxation; the relaxation distribution increases with increase in temperature.     

Synthesis, crystal and band structures, and optical properties of a new framework mercury pnictides: [Hg4As2](InBr3.5As0.5) with tridymite topology

A new framework compound, [Hg₄As₂](InBr_3.5As_0.5) (1), has been prepared by the solid-state reaction of Hg₂Br₂ with elemental In and As at 450 °C. Compound 1 crystallizes in the space group P₆₃/mmc of the Hexagonal system with two formula units in a cell: a = b = 7.7408(6) Å, c = 12.5350(19) Å, V = 650.47(12) Å³. The crystal structure of 1 features a novel 3D framework, [Hg₄As₂]²⁺ with tridymite topology. The optical properties were investigated in terms of the diffuse reflectance and infrared spectra. The electronic band structure along with density of states (DOS) calculated by DFT method indicates that the present compound is semiconductor, and the optical absorption is mainly originated from the charge transitions from Br-4p and As-4p states to Hg-6s and In-5p states.     

Synthesis and structure determination of In3TeO3F7: An indium oxyfluorotellurate IV derived from W bronze structure with Te in hexagonal tunnels

After InTeO₃F and InTe₂O₅F recently described, a new compound In₃TeO₃F₇ is characterized in the In-Te^IV-O-F system. The crystal structure was determined by single X-ray diffraction and refined to R₁ = 0.028. In₃TeO₃F₇ crystallizes in orthorhombic space group Cmmm, a = 7.850(2) Å, b = 27.637(6) Å, c = 4.098(1) Å, V = 889.1(4) Å³ and Z = 4. Its structure consists of the stacking, via vertices, of identical layers composed of InF₆ and InO₂F₄ octahedra sharing corners and of InO₄F₃ pentagonal bipyramids sharing edges and vertices. The Te cations statistically occupy one or the other of two close sites located inside tunnels delimited by the In polyhedra and are bonded to F anions located in the same tunnels.The structure can be considered as an intergrowth of parallel strips of MIn₃F₁₀ and hexagonal tungsten bronze (c)-types. It is compared to other structures such as the bronze Sb_0.157WO₃, TeMo₅O₁₆ and Sb₂Mo₁₀O₃₁, phases also comprising Te⁴⁺ or Sb³⁺ inside hexagonal tunnels. The electronic lone pair of Te⁴⁺ is stereochemically active and a perfect O/F ordering occurs on the anionic sites.     

CuIn1−xAlxS2 thin films prepared by sulfurization of metallic precursors

CuIn_1−xAl_xS₂ thin films (x = 0, 0.09, 0.27, 0.46, 0.64, 0.82 and 1) with thicknesses of approximately 1 μm were formed by the sulfurization of DC sputtered Cu-In-Al precursors. All samples were sulfurized in a graphite container for 90 min at 650 °C in a 150 kPa Ar + S atmosphere. Final films were studied via X-ray diffraction (XRD), scanning electron microscopy (SEM) and micro-Raman spectroscopy. It was found that all samples were polycrystalline in nature and their lattice parameters varied slightly nonlinearly from {a = 5.49 Å, c = 11.02 Å} for CuInS₂ to {a = 5.30 Å, c = 10.36 Å} for CuAlS₂. No unwanted phases such as Cu_2−xS or others were observed. Raman were recorded at a room temperature and the most intensive and dominant A₁ phonon frequency varied nonlinearly from 294 cm⁻¹ (CuInS₂) to 314 cm⁻¹ (CuAlS₂).     

Isothermal section of the Ag2S-PbS-GeS2 system at 300 K and the crystal structure of Ag2PbGeS4

The isothermal section of the Ag₂S-PbS-GeS₂ system at room temperature was investigated by XRD. The existence of two quaternary compounds, Ag₂PbGeS₄ and Ag_0.5Pb_1.75GeS₄, was confirmed, and the phase equilibria between the binary system components and the ternary and the quaternary compounds were determined. The crystal structure of Ag₂PbGeS₄ was studied using the single crystal X-ray diffraction. It was established that Ag₂PbGeS₄ crystallizes in an own structural type in non-centrosymmetric space group Ama2 with the lattice parameters a = 1.02390(4) nm, b = 1.02587(5) nm, c = 0.67701(3) nm.     

Fabrication of GdBa2Cu3O7−x films by TFA-MOD process

GdBa₂Cu₃O_7−x (GdBCO) films have been deposited on LaAlO₃ (LAO) (0 0 l) single crystal substrates by trifluoroacetate metal organic deposition (TFA-MOD) method. The effects of oxygen partial pressure and firing temperature on microstructure and critical properties of GdBCO films were discussed. The phase formation, texture and microstructure of films were characterized by X-ray diffraction and scanning electron microscopy. The oxygen partial pressure was considered to play a great role for formation of impurity phase and a-axis oriented grains. The degree of c-axis orientation was also influenced by the firing temperature. The highly c-axis oriented GdBCO film obtained at 815 °C under an oxygen partial pressure of 100 ppm has a high performance critical current density J_c (77 K, self field) = 1.8 MA/cm².     

Synthesis, characterization, shape-preserved transformation, and optical properties of La(OH)3, La2O2CO3, and La2O3 nanorods

A simple method to directly synthesize stable and crystalline pure phase La(OH)₃ nanorods, with a diameter of around 15 nm and lengths in the range of 120-200 nm, was developed using cationic surfactant (cetyltrimethylammonium bromide, CTAB). The obtained La(OH)₃ nanorods can be successfully converted to La₂O₂CO₃ and La₂O₃ nanorods via calcination under appropriate conditions. Analytical methods such as X-ray diffraction (XRD) spectra, Fourier transformed infrared (FTIR) spectrum, differential scanning calorimetry and thermogravimetric analysis (DSC-TGA), transmission electron microscopy (TEM), and high-resolution TEM (HRTEM) were employed to characterize the morphology and microstructure of the final products. The results reveal that La(OH)₃ nanorods were shape-preserved and transformed to La₂O₂CO₃ nanorods at 400 °C for 2 h and to La₂O₃ nanorods at 800 °C for 2 h, respectively. TEM images indicate that the as-obtained La₂O₂CO₃ and La₂O₃ entirely consist of uniform nanorods in high yield with diameters of about 15 nm and 23 nm, lengths of 200-300 nm and 300-500 nm, respectively. The formation mechanism of the La(OH)₃, La₂O₂CO₃ and La₂O₃ nanorods was investigated. Room-temperature photoluminescence (RTPL) properties were investigated under the excitation of 275 nm. The ⁵D₃ → ⁷F_j (j = 2-6) emission peaks at the wavelength below 500 nm were found in the RTPL spectra.     

Microwave dielectric properties and its compatibility with silver electrode of Li2MgTi3O8 ceramics

The effects of BaCu(B₂O₅) (BCB) additions on the sintering temperature and microwave dielectric properties of Li₂MgTi₃O₈ ceramic have been investigated. The pure Li₂MgTi₃O₈ ceramic shows a relative high sintering temperature (∼1000 °C) and good microwave dielectric properties as Q × f of 40,000 GHz, ?_r of 27.2, τ_f of 2.6 ppm/°C. It was found that the addition of a small amount of BCB can effectively lower the sintering temperature of Li₂MgTi₃O₈ ceramics from 1025 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 0.5 wt% BCB added Li₂MgTi₃O₈ ceramic sintered at 900 °C for 2 h exhibited good microwave dielectric properties of Q × f = 36,200 GHz (f = 7.31 GHz), ?_r = 26 and τ_f = −2 ppm/°C. Compatibility with Ag electrode indicates this material can be applied to low temperature-cofired ceramics (LTCC) devices.     

Microstructure and electrical properties of PLZT ceramics from Pb3O4 as the lead source

In this paper, Pb₃O₄, rather than conventional PbO, was introduced in the solid phase synthesis of (Pb_0.92La_0.08)(Zr_0.35Ti_0.65)_0.98O₃ (PLZT) ceramics. The microstructure and electrical properties of the PLZT ceramics were investigated. Results showed that due to the activity of Pb₃O₄, pyrochlore phase PLZT was depressed effectively. The PLZT ceramics with 5.0 wt.% excess Pb₃O₄ in the original materials had a well-crystallized pure perovskite structure when being sintered at 1100 °C for 6 h. In addition, the amount of Pb₃O₄ had an influence on the electrical properties of the PLZT ceramics. Residual polarization as high as 36.9 μC/cm² was obtained from the samples with 5.0 wt.% excess Pb₃O₄.     

Multiwavelength excited novel red-emitting phosphor Eu-activated Li2Zn2(MoO4)3

Eu³⁺-activated Li₂Zn₂(MoO₄)₃ multiwavelength excited red-emitting phosphors were synthesized via a solid state reaction. The structure and photoluminescence characteristics were investigated by X-ray powder diffraction and fluorescent spectrophotometry, respectively. The excitation spectrum included a strong broadband ranging from 250 to 350 nm and some sharp peaks at 363, 384, 395, 465, and 533 nm, which matchs the radiations of near-UV or blue light-emitting diodes chip well. Upon excitation either of near-UV or blue even green light, the intense red emission with 615 nm peak can be observed, which is ascribed to the ⁵D₀-⁷F₂ transition of Eu³⁺ ions. The chromaticity coordinates (x = 0.65, y = 0.34) of the as-obtained phosphor is very close to the National Television Standard Committee standard values (x = 0.67, y = 0.33). All these characteristics suggest that Eu³⁺-doped Li₂Zn₂(MoO₄)₃ wavelength-conversion material to be suitable candidate red component for phosphor-converted white light-emitting diodes.     

Synthesis, structure and optical properties of CoAl2O4 spinel nanocrystals

CoAl₂O₄ nanocrystals were synthesized by sol-gel method using citric acid as a chelating agent at low temperature. The as-synthesized samples were characterized by thermal analysis, X-ray powder diffraction, infrared spectroscopy and transmission electron microscopy. The results show that CoAl₂O₄ spinel is the only crystalline phase with a size of 10-30 nm in the temperature range 500-1000 °C. The temperature dependence of the distribution of Al³⁺ and Co²⁺ ions in the octahedral and tetrahedral sites in nanocrystals was investigated by X-ray photoelectron spectroscopy (XPS). It is observed that the inversion parameter decreases with increasing annealing temperature. Analysis of the absorption properties indicates that Co²⁺ ions are located in the tetrahedral sites as well as in the octahedral sites in the CoAl₂O₄ nanocrystals. The origin of the green color (300-500 nm absorption band) should be due to the octahedrally coordinated Co²⁺ ions.     

High-Q microwave dielectrics in the (Mg1−xZnx)Al2O4 (x = 0-0.1) system

The microwave dielectric properties and the microstructures of (Mg_1−xZn_x)Al₂O₄ (x = 0-0.1) ceramic system prepared by the conventional solid-state route were investigated. The forming of spinel-structured (Mg_1−xZn_x)Al₂O₄ (x = 0-0.1) solid solutions was confirmed by the XRD patterns and the measured lattice parameters, which linearly varied from a = b = c = 8.0815 Å for MgAl₂O₄ to a = b = c= 8.0828 Å for (Mg_0.9Zn_0.1)Al₂O₄. By increasing x, the Q × f of (Mg_1−xZn_x)Al₂O₄ can be tremendously boosted from 82,000 GHz at x = 0 to a maximum of 156,000 GHz at x = 0.05. The Zn substitution was effective in reducing the dielectric loss without detrimental effects on the ?_r and τ_f values of the ceramics.