Synthesis,crystal structure and dielectric properties of C6H18N2SbCl5

The result of the X‐ray diffraction, differential scanning calorimetry and dielectric studies on a new crystal material C₆H₁₈N₂SbCl₅ is presented. The new organic–inorganic compound has been synthesized and characterized by the X‐ray diffraction method at 296(2) K. It crystallizes in the monoclinic P21/n space group. The cell dimensions are: a = 5.8617(1) Å, b = 15.7069(2) Å, c = 16.6693(2) Å, β = 97.627(1)° and Z = 4. The crystal structure consists of a discrete ionic layer of (C₆H₁₈N₂)²⁺ cations and [SbCl₅]^2? anions linked via simple and bifurcated N―H · · · Cl hydrogen bonds. DSC analysis shows that this compound undergoes a phase transition at about (384 ± 2) K. AC and DC conductivities, complex dielectric permittivity ε*(ω) and complex electrical modulus M*(ω) were respectively studied as temperature and frequency functions. The combined data support each other and confirm the existence of a structural phase transition at about 384 K. Moreover, the temperature dependence of the DC conductivity and relaxation frequency followed the Arrhenius relation. The frequency dependence of the real part of the AC conductivity in both phases follows the Jonscher's universal dynamic law: . The behavior of s(T) with temperature suggests that the hopping over barrier model (CBH) and the small polaron tunneling mechanism (SPTM) prevail in phases I and II, respectively. Copyright © 2016 John Wiley & Sons, Ltd.     

Magnetic and electric studies of a new Co(II) perovskite-like material

Structural phase transitions in the perovskite-like material [(CH₄)₁₂(NH₃)₂]CoCl₄ have been observed using differential thermal scanning. The material shows an order-disorder transition at T ₁ = 396 ± 5 K with entropy, (ΔS ₁) = 12.8 J/mole/K. A "chain melting" transition with a major endothermic peak at T ₂ = 337 ± 3 K and a minor one at T ′ = 316 ± 2 K, has total entropy ΔS = 28 J/mole/K. At low temperatures, the transitions at T ₃ = 288 ± 3 K and at T ₄ = 188 ± 3 K, have entropies of ΔS ₃ = 14.4 J/mole/K and ΔS ₄ = 2.6 J/mole/K respectively. AC magnetic susceptibility in the temperature range 78-290 K, in a magnetic field of 160 A/m and at a frequency of 320 Hz is presented. The results indicate changes in symmetry at 188 K. Dielectric permittivity has been studied as a function of temperature in the range 300-430 K and frequency range (60 Hz-100 kHz), confirming the observed transitions. The dielectric permittivity reflects rotational and conformational transition for the material. The variation of the real part of the conductivity with temperature is thermally activated with different activation energies in the range of ionic hopping. The temperature dependence of the dc conductivity and that of the ions hopping rate have indicated that the concentration of mobile ions is independent of temperature. The dependence of the conductivity on frequency follows the universal power law, <artwork name="GPHT31040ei1"> in the temperature range 340 K<T<390 K. Values 0 <s ₁ <1 dominate at low frequency and correspond to translational hopping motion and values 1<s ₂<2 dominate at high frequencies and correspond to well localized hopping and/or reorientational motion. For T > 396 K, the AC conductivity was fitted to <artwork name="GPHT31040ei2"> with 0<s<1. Comparison with the corresponding Cu-containing material is discussed.     

Oxidation of nickel and transport properties of nickel oxide

Oxidation kinetics of high purity nickel, as well as the nonstoichiometry and chemical diffusion in nickel oxide have been studied as a function of temperature (1373-1673 K) and oxygen pressure (10-10⁵ Pa) using microthermogravimetric techniques. In order to eliminate the possible participation of grain boundary diffusion in scale growth at lower temperatures, the oxidation rate measurements have always been started at the highest temperature (1673 K), when coarse-grained scale was formed, and the temperature and pressure dependence of the oxidation rate was determined by step-wise lowering the temperature of such pre-oxidized sample. Nonstoichiometry and the chemical diffusion coefficient in Ni_1−yO have also been determined on such coarse-grained oxide samples, obtained by complete oxidation of nickel at highest temperature (1673 K). It has been found, that under such conditions oxidation of nickel follows strictly the parabolic rate law, and the parabolic rate constant of this reaction is the following function of temperature and oxygen pressure: The results of nonstoichiometry measurements, in turn, may be described by the following relationship Finally, chemical diffusion coefficient in Ni_1−yO has been found to be independent on oxygen activity, indicating that the mobility of point defects in this oxide does not depend on their concentration, being the following function of temperature: It has been shown, that the parabolic rate constants of nickel oxidation, calculated from nonstoichiometry and chemical diffusion data are in excellent agreement with experimentally determined k_p values. All these results clearly indicate that the predominant defects in nonstoichiometric nickel oxide (Ni_1−yO) are double ionized cation vacancies and electron holes and the oxide scale on nickel growths by the outward volume diffusion of cations.     

Electrical transport properties of Ag3Sn compound

The temperature behaviors of the electrical resistivity in polycrystalline Ag₃Sn bulk samples were investigated experimentally. We found that the temperature dependence of resistivity shows concave function characteristics from 305 down to 26 K, and can be described by a parallel resistor model [H. Wiesmann et al., Phys. Rev. Lett. 38 (1977) 782]. The resistivities of all samples reveal T² behavior from 26 down to . We compared our data to the existing theories in which the T² dependence of resistivity has been proposed. However, we found none of them can describe the experimental data, and the physical mechanism of the T² behavior of resistivity at low temperatures is still enigmatical.     

Electronic properties of single-crystal diamonds heavily doped with boron

Single-crystal diamonds with characteristic sizes of 2–7 mm doped with boron in the concentration range 10¹⁹–10²⁰ cm^?3 have been grown by the temperature gradient method at high static pressures. The temperature dependence of the resistance R of the synthesized single crystals has been measured in the range 0.5 K < T < 297 K. An activated dependence R(T) with an activation energy of about 50 meV is observed in the range from room temperature to T ≈ 200 K. At temperatures below approximately 50 K, the temperature dependence of the conductivity for heavily doped crystals is proportional to T ^1/2, which is characteristic of degenerate semiconductors with a high number of defects.     

Antiferromagnetic transition and electrical conductivity in α-Gd2S3

Magnetic susceptibility and electrical resistivity of α-Gd₂S₃ with an orthorhombic structure (space group: Pnma) have been measured for powder and single-crystal samples. While the magnetic susceptibility of powder sample exhibits a broad peak having a maximum at 4.2 K, the susceptibility for a single crystal with an applied magnetic field along the b-axis demonstrates a sharp drop below 10 K. Nevertheless, the susceptibility with the field perpendicular to the b-axis keeps increasing with decreasing temperature even below 10 K. The electrical resistivity ρ for the powder sample of 4.2×10³ Ω cm around room temperature increases with decreasing temperature and shows a slight discontinuity at about 65 K. In both regions above and below 65 K, is proportional to T^−1/4 with respective coefficients, which is associated with Mott variable-range hopping conductivity. The resistivity of a single crystal along the b-axis is considerably smaller than the value for the powder sample as 0.35 Ω cm at room temperature, and its temperature dependence is fairly weak. While cooling, the resistivity first decreases down to 240 K and then keeps the value independent of the temperature down to 140 K, and subsequently rises gently below 140 K.     

AC conductivity and mechanism of conduction study of lithium barium pyrophosphate Li<Subscript>2</Subscript>BaP<Subscript>2</Subscript>O<Subscript>7</Subscript> using impedance spectroscopy

The Li₂BaP₂O₇ compound has been obtained by the conventional solid-state reaction and characterized by X-ray powder diffraction. The title material crystallizes in the monoclinic system with C2/c space group. Electrical properties of the compound have been studied using complex impedance spectroscopy in the frequency range 200 Hz–5 MHz and temperature range 589–724 K. Temperature dependence of the DC conductivity and modulus was found to obey the Arrhenius law. The obtained values of activation energy are different which confirms that transport in the titled compound is not due to a simple hopping mechanism. AC conductivity measured follows the power-law dependence σ _AC?～?ω ^s typical for charge transport. Therefore, the experimental results are analyzed with various theoretical models. Temperature dependence of the power law exponent s strongly suggests that tunneling of large polarons is the dominant transport process.     

A study on new phase transitions in Cs2CaCl4·2H2O single crystals by observation of Cs NMR

The ¹³³Cs 1/2→−1/2 spin-lattice relaxation rate, , and the spin-spin relaxation rate, , for a Cs₂CaCl₄·2H₂O single crystal have been measured in function of temperature. The dominant relaxation mechanism of this crystal over the whole temperature range investigated here proceeds via quadrupole interaction. The changes in the ¹³³Cs spin-lattice relaxation rate near 325 K (=T_c1) and 360 K (=T_c2) correspond to phase transitions in the crystal. The change in the spin-lattice relaxation rate at T_c1 is small because the crystal lattice does not change very much during this phase transition. The change in near T_c2 is due to the critical slowing down of the soft mode that typically occurs in structural phase transitions. The temperature dependence of the spin-lattice relaxation rate for this crystal has maximum values at about 240 K, which is attributable to the effect of molecular motion as described by Bloembergen-Purcell-Pound theory. The phase transition temperatures T_c1 and T_c2 obtained from the temperature dependence of the relaxation rate is also clear from data obtained using differential scanning calorimetry. Therefore, we know that previously unreported phase transitions occur at 325 and 360 K.     

Mn1−xFexIn2Se4: a new layered semiconductor system

Mn_1−xFe_xIn₂Se₄ compounds (x=0.1; x=0.7) were grown by the chemical vapor transport method. X-ray diffraction analysis data show that these compositions crystallize as different polytypes that belong to the hexagonal structure. The crystal symmetry of the sample with x=0.1 belongs to the space group Rm and for the sample with x=0.7 the space group is P6₃mc.The magnetic behavior of both samples has been investigated in the temperature range between 5 and 300 K. Spin-glass-like behavior below the freezing temperature T_f=9 K has been found for the sample with x=0.7. The sample with Fe content x=0.1 behaves as a paramagnet down to the lowest experimental measured temperature. High-temperature susceptibility data follow the Curie-Weiss law with a negative paramagnetic temperature indicating predominant antiferromagnetic interactions.Optical studies reveal that both samples (x=0.1; 0.7) are direct band gap semiconductors. The temperature dependence of the energy gap fits Varshni relation quite well.     

Muon spin rotation in orthoferrites ErFeO3 and DyFeO3

SR measurements on the rare earth orthoferrites ErFeO₃ and DyFeO₃ are reported. Experiments have been made as a function of temperature (8–460 K) and the external magnetic field. Above 90 K a single internal field on the order of 2 kG parallel to the c-direction is observed. Zero external field measurements between 50 K and 84 K showed in ErFeO₃ two distinct local fields. The external field dependence of the observed frequencies demonstrates that the local field is related to the weak ferromagnetism in both orthoferrites.Work supported by the Swiss National Science Foundation.     

Li<Superscript>+</Superscript> ion conductivity and transport properties of LiYP<Subscript>2</Subscript>O<Subscript>7</Subscript> compound

A lithium yttrium diphosphate LiYP₂O₇ was prepared by a solid-state reaction method. Rietveld refinement of the X-ray diffraction pattern suggests the formation of the single phase desired compound with monoclinic structure at room temperature. The infrared and Raman spectrum of this compound was interpreted on the basis of P₂O₇ ^4? vibrations. The AC conductivity was measured in the frequency range from 100 to 10⁶ Hz and temperatures between 473 and 673 K using impedance spectroscopy technique. The obtained results were analyzed by fitting the experimental data to the equivalent circuit model. The Cole–Cole diagram determined complex impedance for different temperatures. The angular frequency dependence of the AC conductivity is found to obey Jonscher’s relation. The temperature dependence of σ _AC could be described in terms of Arrhenius relation with two activation energies, 0.87 eV in region I and 1.36 eV in region II. The study of temperature variation of the exponent(s) reveals two conduction models: the AC conduction dependence upon temperature is governed by the correlated barrier hopping (CBH) model in region I (T < 540 K) and non-overlapping small polaron tunneling (NSPT) model in region II (T > 540 K). The near value of activation energies obtained from the equivalent circuit and DC conductivity confirms that the transport is through ion hopping mechanism dominated by the motion of the Li⁺ ion in the structure of the investigated material.     

Synthesis and properties of high-pressure phase [Er<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>](V<Subscript>4</Subscript>)O<Subscript>12</Subscript>

A new perovskite-like compound Er_0.73Cu₃V₄O₁₂ (space group Im \(\bar 3\), Z = 2, a = 7.266 Å) has been synthesized barothermally (P = 8.0 GPa, t = 1000°C). Its electrical and magnetic properties have been studied. It is found that the temperature dependence of the electrical conductivity (in the range 78–300 K) has of semiconductor type. The behavior of the impedance and admittance has been analyzed at 290 K and frequencies of 200 Hz to 200 kHz under atmospheric pressure and at high (15–42 GPa) pressures.     

Structural and magnetic characterization of rhombohedral Ga1.2Fe0.8O3 ceramics prepared by high-pressure synthesis

The rhombohedral α- Ga_1.2Fe_0.8O₃ ceramics have been synthesized by using a high pressure technique at a pressure of 5 GPa and a temperature of 800 °C from orthorhombic ε- Ga_1.2Fe_0.8O₃ ceramics, which were identified to be isostructural with α- Fe₂O₃ and α- Ga₂O₃. The low temperature magnetism has been studied for α- Ga_1.2Fe_0.8O₃, the saturation magnetization is at 5 K, and the Morin temperature has not been found. Moreover, it is most probable that the spin reorientation of α- Ga_1.2Fe_0.8O₃ has been found at 50 K resulted from the change of magnetic dipole anisotropy and single-ion anisotropy with temperature.     

Local features of the crystal structure of superconducting iron chalcogenides Fe(TeSe)<Subscript>1 – δ</Subscript>

The local crystal structure of superconducting powders of iron chalcogenides FeTe_xSe_1–x (x = 0.1, 0.22, 0.49, 0.8, 0.9) prepared by dry synthesis (without mineralizer) has been studied by EXAFS spectroscopy above the K Se and K Fe absorption edges in the temperature range of 80–300 K. The dependences of Se–Fe, Fe–Te, and Fe–Fe interatomic bond lengths and degrees of their local disordering (Debye–Waller factors) on the tellurium content and temperature have been obtained. Einstein temperatures characterizing the stiffness of each bond have been determined. The correlation of the Se–Fe bond stiffness with the dependence of the critical temperature of the superconducting transition T_c on the composition of the samples under study have been established, which indicates the specific role of the Se–Fe bond in the superconducting state formation in iron chalcogenides FeTe_xSe_1–x.     

Intercluster conduction in lightly doped La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> manganites in the paramagnetic temperature range

The magnetotransport and magnetic properties of La _{1 ? x} Ca _x MnO₃ polycrystalline samples (x = 0–0.3) annealed under vacuum and in the oxygen environment are investigated in the temperature range from 77 to 400 K. The magnetic studies of lightly doped manganites reveal persistence of short-range magnetic order up to a temperature T* ≈ 300 K, which is about 2–3 times higher than their Curie temperature T _C. The temperature dependence of the electrical resistivity measured from T* down to nearly T ≈ T _C is fitted by the relation logρ ～ T ^?1/2, which is characteristic of granular metals with electrons tunneling among nanoclusters of magnetic metals embedded in a dielectric host. The magnetoresistance of polycrystalline samples annealed in the oxygen environment has been observed to increase. The electrical, magnetic, and magnetotransport properties of the manganites can be accounted for by the formation of magnetic nanoclusters below T*, tunneling (or hopping) of carriers among the nanoclusters, variation in the magnetic cluster size, and tunneling barrier thickness with variations in temperature and magnetic field strength, as well as by the effect of annealing in different media on the cluster properties.     

Non-Fermi liquid behavior in polycrystalline Ce2PdIn8

We report on the formation of a novel ternary compound Ce₂PdIn₈ that is isostructural with the heavy-fermion superconductors Ce₂CoIn₈ and Ce₂RhIn₈. Its magnetic, electrical transport and thermodynamic properties were studied on polycrystalline samples in wide ranges of temperature and magnetic field strength. The results revealed Ce₂PdIn₈ to be a paramagnetic Kondo lattice with a coherence temperature of about 12 K. The C/T ratio of the specific heat reaches at 350 mK a strongly enhanced magnitude of about per Ce-atom, thus clearly indicating a heavy-fermion nature of this material. Moreover, a logarithmic divergence of C/T vs. T, observed below 3 K, which is accompanied by a linear temperature dependence of the electrical resistivity below 6 K, hint at a non-Fermi liquid character of the electronic ground state in the new compound reported.