Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

Improved GaSb surfaces using a (NH4)2S/(NH4)2S04 solution

Bulk (1 0 0) n-GaSb surfaces have been treated with a sulphur based solution ((NH₄)₂S/(NH₄)₂SO₄) to which sulphur has been added, not previously reported for the passivation of GaSb surfaces. Au/n-GaSb Schottky barrier diodes (SBDs) fabricated on the treated material show significant improvement compared to that of the similar SBDs on the as-received material as evidenced by the lower ideality factor (n), higher barrier height (?_b) and lower contact resistance obtained. Additionally, the reverse leakage current, although not saturating, has been reduced by almost an order of magnitude at −0.2 V. The sample surfaces were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The native oxide, Sb–O, present on the as-received material is effectively removed on treating with ([(NH₄)₂S/(NH₄)₂SO₄]+S) and (NH₄)₂S. Analysis of the as-received surface by XPS, prior to and after argon sputtering, suggests that the native oxide layer is ≤8.5 nm.     

EPR studies of linewidth anomalies at phase transitions in [N(C2H5)4]2MnCl4

We have studied [N(C₂H₅)₄]₂MnCl₄ crystal by X-band CW EPR spectra in the temperature range 170-300 K. The angular dependences of linewidth ΔH were measured and described in the light of a double-layer system (2D) with exchange interactions. Two temperature anomalies of linewidth ΔH were found at T₁=225 K and T₂=192 K on cooling. Different behaviors of ΔH anomalies recorded for an external magnetic field parallel and perpendicular to the ab crystallographic plane indicate ordering/disordering of MnCl₄ groups in this plane and their displacement along the c-axis which occurs in the temperature of about 225 K.     

Electron surface states in short-period superlattices: (GaAs)2/(AlAs)2(1 0 0)-c(4 × 4)

The electronic structure of (GaAs)₂/(AlAs)₂(1 0 0)-c(4 × 4) superlattice surfaces was studied by means of angular-resolved photoelectron spectroscopy (ARUPS) in the photon energy range 20-38 eV. Four samples with different surface termination layers were grown and As-capped by molecular beam epitaxy (MBE). ARUPS measurements were performed on decapped samples with perfect c(4 × 4) reconstructed surfaces. An intensive surface state was, for the first time, observed below the top of the valence band. This surface state was found to shift with superlattices’ different surface termination in agreement with theoretical predictions.     

Thermoelectric power of TTF[Ni(dmit)2]2

The 1D organic salt TTF[Ni(dmit)₂]₂ becomes superconductor with T_c=1.6 K under an applied hydrostatic pressure of 7 kbar. Structural determinations in this system lead us to suspect that superconductivity (SC) coexists with a charge density wave (CDW) instability at low pressure. In order to better understand how SC emerge from a CDW and to revisit the pressure–temperature phase diagram of the TTF[Ni(dmit)₂]₂ we performed transport and thermoelectric power measurements under pressure.     

Synthesis and characterization of Co7(OH)12(C2H4S2O6)(H2O)2—a single crystal structural study of a ferrimagnetic layered cobalt hydroxide

A novel layered hydrotalcite-like material, Co₇(H₂O)₂(OH)₁₂(C₂H₄S₂O₆), has been prepared hydrothermally and the structure determined using single crystal X-ray diffraction (a=6.2752(19) Å, b=8.361(3) Å, c=9.642(3) Å, α=96.613(5)°, β=98.230(5)°, γ=100.673(5)°, R1=0.0551). The structure consists of brucite-like sheets where 1/6 of the octahedral sites are replaced by two tetrahedrally coordinated Co(II) above and below the plane of the layer. Ethanedisulfonate anions occupy the space between layers and provide charge balance for the positively charged layers. The compound is ferrimagnetic, with a Curie temperature of 33 K, Curie-Weiss θ of −31 K, and a coercive field of 881 Oe at 5 K.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

Crystal structure and ferromagnetism of (n-C3H7)4N[CoFe(dto)3] (dto=C2O2S2)

Recently, we have discovered a new type of first order phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto=C₂O₂S₂), where the charge transfer transition between Fe^II and Fe^III occurs reversibly. In order to elucidate the origin of this peculiar first order phase transition. Detailed information about the crystal structure is indispensable. We have synthesized the single crystal of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃] whose crystal structure is isomorphous to that of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃], and determined its detailed crystal structure. Crystal data: space group P6₃, a=b=10.044(2) Å, c=15.960(6) Å, α=β=90°, γ=120°, Z=2 (C₁₈H₂₈NS₆O₆FeCo). In this complex, we found a ferromagnetic transition at T_c=3.5 K. Moreover, on the basis of the crystal data of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃], we determined the crystal structure of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] by simulation of powder X-ray diffraction results.     

Electrical properties of SrBi2(Nb0.5Ta0.5)2O9 ceramics

Aurivillius SrBi₂(Nb_0.5Ta_0.5)₂O₉ (SBNT 50/50) ceramics were prepared using the conventional solid-state reaction method. Scanning electron microscopy was applied to investigate the grain structure. The XRD studies revealed an orthorhombic structure in the SBNT 50/50 with lattice parameters a=5.522 Å, b=5.511 Å and c=25.114 Å. The dielectric properties were determined by impedance spectroscopy measurements. A strong low frequency dielectric dispersion was found to exist in this material. Its occurrence was ascribed to the presence of ionized space charge carriers such as oxygen vacancies. The dielectric relaxation was defined on the basis of an equivalent circuit. The temperature dependence of various electrical properties was determined and discussed. The thermal activation energy for the grain electric conductivity was lower in the high temperature region (T>303.6 °C, E_a−ht=0.47 eV) and higher in the low temperature region (T<303.6 °C, E_a−lt=1.18 eV).     

A new sodium samarium borate Na3Sm2(BO3)3

A new sodium samarium borate with composition Na₃Sm₂(BO₃)₃ (NSBO) has been synthesized by high temperature solid state reaction. The yellowish transparent single crystals of Na₃Sm₂(BO₃)₃ have been grown from the Na₂CO₃-H₃BO₃ flux system using the top-seeded solution growth (TSSG) method. X-ray diffraction analysis demonstrated that the NSBO crystals belong to orthorhombic systems and lattice parameters are a=5.0585 Å, b=11.0421 Å, c=7.0316 Å. The measurement of the infrared spectrum indicated that the basic anionic groups are the BO³⁻₃ groups. Furthermore, Na₃Sm₂(BO₃)₃ exhibits an optical second harmonic generation effect which is close to that of KDP (KH₂PO₄).     

Effect of surface-topology on magnetic properties in (La0.6Eu0.4)0.67Ca0.33MnO3 of anisotropic shape of nanoplates

(La_0.6Eu_0.4)_0.67Ca_0.33MnO₃ has been prepared in the shape of nanoplates of single crystallites (an orthorhombic structure) through polymer templates. HRTEM images reveal 18, 25, and 30 nm thicknesses of plates after heating a precursor powder at 873, 1073, and 1273 K in air for 2 h. These values present average crystallite size determined from broadening of the X-ray diffraction peaks. A spin-glass-like surface (GS) overlayer (3-5 nm thickness) in such plates facilitates a ferromagnetic→ferrimagnetic reordering with markedly suppressed Curie point T_C, i.e., as small as 90 K in a 873 K heated sample, from the parent value 268 K. The T_C point increases to 103 K (or 120 K) when heating at higher temperature 1073 (or 1273 K), during which the core grows at the expense of the overlayer. The GS tailors as high coercivity H_c as 617 Oe in the zero field cooled (ZFC) sample that is decreased to 500 Oe in the field cooled (FC) sample in the surface spin-freezing along the field direction. The H_c-value (ZFC) that steps down successively to 252 Oe on the overlayer is thinned down by heating at 1273 K. Samples heated at 873, 1073, or 1273 K have regularly increased saturation magnetization 35.3, 63.9, or 69.6 emu/g in ZFC, while 43.7, 70.2, or 75.5 emu/g in FC measured at 10 K. The ferrimagnetic reordering are described based on the scenario of an antiferromagnetic exchange coupling between the Eu³⁺ and Mn³⁺ (or Mn⁴⁺) sublattices.     

Effect of composition on the conductivity of CTAB-butanol-octane-nitrate salts (Al(NO3)3 + Zn(NO3)2) microemulsions and on the surface and textural properties of resulting spinels ZnAl2O4

The conductivity σ of a microemulsion series consisting of CTAB + butanol + octane, in which a solution of Al(NO₃)₃ 0.8 M + Zn(NO₃)₂ 0.4 M was gradually added, was studied at room temperature as a function of its composition φ. The addition of nitrate salts solution took place in four different ratios of (butanol + CTAB):octane = 0.2, 0.4, 0.6 and 0.8. Initially, all those four systems are (water in oil, w/o) microemulsions and the gradual addition of the solution of the nitrate salts transforms them to bicontinuous ones. The conductivity increases gradually, but with different rate in each case, and the corresponding critical exponents at the percolation threshold were determined from the curves σ = f(φ). Next at three different compositions of microemulsions, corresponding to ratios (butanol + CTAB):octane = 0.4, 0.6 and 0.8 and ratio of the nitrate salts solution x ≈ 0.25, spinels ZnAl₂O₄ were isolated/prepared. XRD, SEM and N₂ adsorption-desorption measurements were used to determine the structure and texture of those solids. From those measurements the surface area (S_p), the pore volume (V_p), the size of crystallites and the average pore connectivity (c) were found. Those properties showed considerable variation and dependence on the composition of the original microemulsions employed in the preparation, a fact indicating that the structure and texture of the obtained solids can be manipulated at will via the composition of microemulsion used.     

Molecular dynamics of [(CH2OH)3CNH3]2SiF6 by phase transition of 178 K

We have investigated the molecular motions of TRIS⁺ ([(CH₂OH)₃CNH₃]⁺) and ions in the [(CH₂OH)₃CNH₃]₂SiF₆ crystal below room temperature from the measurements of the spin-lattice relaxation time T₁ and the NMR absorption line of ¹H and ¹⁹F nuclei, in order to elucidate the changes of the molecular motions by the phase transition of T_c=178 K. The narrowing of the ¹⁹F-NMR line was observed around T_c=178 K and the reorientation of the anion appears above T_c. Moreover, from the analysis of the temperature dependence of T₁, we have observed that the activation energy of the reorientational motion of ions changes from 0.168 eV (T>T_c) to 0.185 eV (T<T_c). Based on these results, we found that the reorientational motion of ions is closely related to the origin of the phase transition at T_c. In addition, from the measurement of the ¹H-NMR line, we also found that the reorientational motion of H₂ in the -CH₂OH group becomes active accompanied by the phase transition.     

Crystallographic study of the phase transition in (Me4P)2ZnBr4

The compound (Me₄P)₂ZnBr₄, a member of the β-K₂SO₄ structure class, undergoes a phase transition at 84°C from the room temperature space group P12₁/c1 to the parent Pmcn structure. The room temperature structure corresponds to a ferrodistortive transition of B_1g symmetry at the zone center. At room temperature, the compound has lattice constants a=9.501(1), b=16.055(2), c=13.127(2) Å and β=90.43(1)°. For the high temperature phase, the orthorhombic cell has dimensions a=9.466(2), b=16.351(3) and c=13.284(2) Å. The structures consist of two crystallographically independent Me₄P⁺ cations and the ZnBr₄²⁻ anions. In the room temperature phase, all three ionic species show substantial displacement from the mirror plane perpendicular to the a-axis that exists in the high temperature phase, as well as rotations out of that plane. The thermal parameters of the cations are indicative of substantial librational motion. Measurements of lattice parameters have been made at 2-5°C intervals over the temperature range 40-140°C. The changes in the lattice constants appear continuous at T_c (within experimental limits) indicating that the phase transition is likely second-order. The a lattice constant shows an anomalous shortening as T_c is approached. Thermal expansion coefficients are calculated from this data. An application of Landau theory is used to derive the temperature dependencies of spontaneous shear strain and corresponding elastic stiffness constants associated with the primary order parameter.     

Magnetic properties of the novel nanocomposite (Zn0.15Ni0.85Fe2O4)0.15/(SiO2)0.85 at room temperature

The value of the effective magnetic anisotropy constant of the ferrimagnetic nanoparticles Zn_0.15Ni_0.85Fe₂O₄ embedded in a SiO₂ silica matrix, determined through ferromagnetic resonance (FMR), is much higher than the magnetocrystalline anisotropy constant. The higher value of the anisotropy constant is due to the existence of surface anisotropy. However, even if the magnetic anisotropy is high, the ferrimagnetic nanoparticles with a 15% concentration, which are isolated in a SiO₂ matrix, display a superparamagnetic (SPM) behavior at room temperature and at a frequency of the magnetization field equal to 50 Hz. The FMR spectrum of the novel nanocomposite (Zn_0.15Ni_0.85Fe₂O₄)_0.15/(SiO₂)_0.85, recorded at room temperature and a frequency of 9.060 GHz, is observed at a resonance field (B_0r) of 0.2285 T, which is substantially lower than the field corresponding to free electron resonance (ESR) (0.3236 T). Apart from the line corresponding to the resonance of the nanoparticle system, the spectrum also contains an additional weaker line, identified for a resonance field of ∼0.12 T, which is appreciably lower than B_0r. This line was attributed to magnetic ions complex that is in a disordered structure in the layer that has an average thickness of 1.4 nm, this layer being situated on the surface of the Zn_0.15Ni_0.85Fe₂O₄ nanoparticles that have a mean magnetic diameter of 8.9 nm.     

Low temperature synthesis and superconducting properties of polycrystalline T′-(La,Sm)2CuO4

La_2−xSm_xCuO_4+δ with the Nd₂CuO₄ structure was synthesized by precipitation from fused alkaline hydroxide, CsOH, at 400 °C. The as-sintered polycrystalline samples showed no diamagnetic signal, but after post-annealing in vacuum of ≈10⁻⁸ atm at 650–700 °C, the samples with x = 0.1 and 0.3 exhibited superconductivity at T_c on = 25 K. The volume fraction of the superconducting phase estimated from the slope of the Zero-Field-Cooled magnetization data was over 30% for x = 0.3, which confirmed that the La_1.7Sm_0.3CuO_4+δ is a bulk superconductor.     

Crystal structure,ionic conductivity and dielectric relaxation studies in the (C5H10N)2BiBr5 compound

The synthesis and crystal structure of the bis (3-dimethylammonium-1-propyne) pentabromobismuthate(III) salt are given in the present paper. After an X-ray investigation, it has been shown that the title compound crystallizes at 298 K in a centrosymmetric monoclinic system, in the space group C₂/c with the following lattice parameters a=12.9034(3) Å, b=19.4505(6) Å, c=8.5188(2) Å, β=102.449(2). Not only were the impedance spectroscopy measurements of (C₅H₁₀N)₂BiBr₅ carried out from 209 Hz to 5 MHz over the temperature range of 318 K–373 K, but also its ac conductivity evaluated. Besides, the dielectric relaxation was examined using the modulus formalism. Actually, the near values of activation energies obtained from the impedance and modulus spectra confirms that the transport is of an ion hopping mechanism, dominated by the motion of the H⁺ ions in the structure of the investigated material.     

X-ray diffraction, Cs and H NMR and thermal studies of CdZrCs1.5(H3O)0.5(C2O4)4·xH2O displaying Cs and water dynamic behavior

A novel mixed cadmium zirconium cesium oxalate with an open architecture has been synthesized from precipitation methods at room pressure. It crystallizes with an hexagonal symmetry, space group P3₁12 (no. 151), a=9.105(5) Å, c=23.656(5) Å, V=1698(1) Å³ and Z=3. The structure displays a [CdZr(C₂O₄)₄]²⁻ helicoidal framework built from CdO₈ and ZrO₈ square-based antiprisms connected through bichelating oxalates, which generates channels along different directions. Cesium cations, hydronium ions and water molecules are located inside the voids of the anionic framework. They exhibit a dynamic disorder which has been further investigated by ¹H and ¹³³Cs solid-state NMR. Moreover a phase transition depending both upon ambient temperature and water vapor pressure was evidenced for the title compound. The thermal decomposition has been studied in situ by temperature-dependent X-ray diffraction and thermogravimetry. The final product is a mixture of cadmium oxide, zirconium oxide and cesium carbonate.