A new one-dimensional hybrid material lattice: AC conductivity and structural characterization of [C<Subscript>7</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>][CdCl<Subscript>4</Subscript>]

The present paper reports the synthesis, crystal structure, ¹³C and ¹¹¹Cd cross-polarization magic-angle spinning nuclear magnetic resonance(CP-MAS-NMR) analysis and ac conductivity for a new organic–inorganic hybrid salt, [C₇H₁₂N₂][CdCl₄]. The compound crystallizes in the triclinic system, space group P\( \overline 1 \), with unit cell dimensions: a?=?7.1050(3) Å, b?=?8.9579(3) Å, c?=?9.4482(3) Å, α?=?81.415(1)°, β?=?89.710(2)°, γ?=?85.765(1)°, V?=?592.97(4) Å³, and Z?=?2. The asymmetric unit is composed of one-2,4-diammonium toluene cation and one [CdCl₄]^2? anion. The Cd atom is in a slightly distorted octahedra coordination environment. Its structure can be described by infinite chains of CdCl₆ octahedron linked to organic cations by a strong charge-assisted N–H???Cl interactions in order to build organic–inorganic layers staked along \( \left[ {0\overline 1 1} \right] \) direction. The solid state ¹³C CP-MAS-NMR spectra has shown seven isotropic resonances, confirming the existence of seven non-equivalent carbon atoms, which is consistent with crystal structure determined by X-ray diffraction. As for ¹¹¹Cd MAS-NMR, it has shown one cadmium site with isotropic chemical shift observed at 167.2 ppm. The complex impedance of the compound has been investigated in the temperature range of 403–460 K and in the frequency range of 200 Hz–5 MHz. The impedance plots have shown semicircle arcs at different temperatures and an electrical equivalent circuit has been proposed to explain the impedance results. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements.     

Comparative studies of microwave absorption in the singlet paramagnets HoVO<Subscript>4</Subscript> and HoBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> in strong pulsed magnetic fields

Microwave absorption in the tetragonal singlet paramagnets HoVO₄ (zircon structure) and HoBa₂Cu₃O _x (x ≈ 6, layered perovskite structure) is studied and compared in pulsed magnetic fields up to 40 T at low temperatures. These paramagnets are characterized by a singlet-doublet scheme of the low-lying levels of the Ho³⁺ ion in a crystal field. In a magnetic field directed along the tetragonal axis, HoVO₄ exhibits resonance absorption lines at wavelengths of 871, 406, and 305 μm, which correspond to electron transitions between the low-lying levels of the Ho³⁺ ion in the crystal field. The positions and intensities of these absorption lines in HoVO₄ are well described in terms of the crystal-field formalism with the well-known interaction parameters. The absorption spectra of HoBa₂Cu₃O _x at a wavelength of 871 μm exhibit broad resonance absorption lines against the background of strong nonresonance absorption. The effects of low-symmetry (orthorhombic, monoclinic) crystal-field components, the deviation of a magnetic field from a symmetry axis, and various pair interactions on the absorption spectra of the HoVO₄ and HoBa₂Cu₃O _x crystals are discussed. Original Russian Text ? Z.A. Kazeĭ, V.V. Snegirev, M. Goaran, L.P. Kozeeva, M.Yu. Kameneva, 2008, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2008, Vol. 133, No. 3, pp. 632–645.     

Structural transformations of K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals with variations in temperature

Single crystals of the K₃H(SO₄)₂ compound are investigated using X-ray diffraction on Xcalibur S and Bruker diffractometers. The structure of the low-temperature monoclinic phase is refined (space group C2/c, z = 4, a = 14.698(1) Å, b = 5.683(1) Å, c = 9.783(1) Å, β = 103.01(1)°, T = 293 K, Bruker diffractometer), the structural phase transition is revealed, and the structure of the high-temperature trigonal phase is determined (space group R \(\bar 3\) m, z = 3, a = 5.73(1) Å,c = 21.51(1) Å,T = 458 K, Xcalibur diffractometer).     

Thermophysical study of structural phase transitions in Na<Subscript>0.95</Subscript>Li<Subscript>0.05</Subscript>NbO<Subscript>3</Subscript> solid solution

Temperature dependences of specific heat C_p(T) and coefficient of thermal expansion ;(T) for Na_0.95Li_0.05NbO₃ sodium-lithium niobate ceramic samples are investigated in the temperature range of 100–800 K. The C_p(T) and α(T) anomalies at T₃ = 310 ± 3 K, T₂ = 630 ± 8 K, and T₁ = 710 ± 10 K are observed, which correspond to the sequence of phase transitions N ? Q ? S(R) ? T2(S). The effect of heat treatment of the samples on the sequence of structural distortions was established. It is demonstrated that annealing of the samples at 603 K leads to splitting of the anomaly corresponding to the phase transition Q → R/S in two anomalies. After sample heating to 800 K, the only anomaly is observed in both the C_p(T) and ;(T) dependence. Possible mechanisms of the observed phenomena are discussed.     

Magnetic phase diagram and correlation between metamagnetism and superconductivity in Ru<Subscript>0.9</Subscript>Sr<Subscript>2</Subscript>YCu<Subscript>2.1</Subscript>O<Subscript>7.9</Subscript>

The magnetic superconductorRu_0.9Sr₂YCu_2.1O_7.9 (Ru-1212Y) has beeninvestigated using neutron diffraction under variable temperature and magnetic field. Withthe complementary information from magnetization measurements, we propose a magnetic phasediagram T-H for the Ru-1212 system. Uniaxialantiferromagnetic (AFM) order of 1.2μ _B /Ruatoms with moments parallel to the c-axis is found below the magnetictransition temperature at  ~140 K in the absence of magnetic field. In addition,ferromagnetism (FM) in the ab-plane develops below  ~120 K, butis suppressed at lower temperature by superconducting correlations. Externally appliedmagnetic fields cause Ru-moments to realign from the c-axis to theab-plane, i.e. along the ?1,1,0? direction, and induce ferromagnetismin the plane with  ~1μ _B at 60 kOe.These observations of the weak ferromagnetism suppressed by superconductivity and thefield-induced metamagnetic transition between AFM and FM demonstrate not only competingorders of superconductivity and magnetism, but also suggest a certain vortex dynamicscontributing to these magnetic transitions.     

Raman scattering spectroscopy of inclusions of carbon in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> films and its solid solutions with HfO<Subscript>2</Subscript>

We apply Raman scattering spectroscopy to study the nature of carbon inclusions in Al₂O₃ and (HfO₂) _x (Al₂O₃)_{1 ? x} films deposited using volatile complex compounds. Raman spectra of the films under investigation contain D and G vibrational modes, which indicate that carbon clusters of the sp ² configuration tend to form in the films. We estimate the size of clusters from the integrated intensity ratio I _D /I _G and find it to be in the range of 14–20 Å. The content of hydrogen in carbon clusters is calculated from the height of the photoluminescence pedestal and is found to vary from 14 to 30 at % depending on the regime of the film’s synthesis.     

High-resolution spectroscopy of HoFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a study of phase transitions

The transmission spectra of HoFe₃(BO₃) multiferroic single crystals are studied by optical Fourier-transform spectroscopy at temperatures of 1.7–423 K in polarized light in the spectral range 500–10 000 cm^–1 with a resolution up to 0.1 cm^–1. A new first-order structural phase transition close to the second-order transition is recorded at T_c = 360 K by the appearance of a new phonon mode at 976 cm^–1. The reasons for considerable differences in T_c for different samples of holmium ferroborate are discussed. By temperature variations in the spectra of the f–f transitions in the Ho³⁺ ion, we studied two magnetic phase transitions, namely, magnetic ordering into an easy-plane structure as a second-order phase transition at T_N = 39 K and spin reorientation from the ab plane to the c axis as a first-order phase transition at T_SR = 4.7 ± 0.2 K. It is shown that erbium impurity in a concentration of 1 at % decreases the spin-reorientation transition temperature to T_SR = 4.0 K.     

High-frequency EPR of Cr<Superscript>2+</Superscript> ions in CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript>

High-frequency broad-band (65–240 GHz) EPR is used to study impurity centers of bivalent chromium in a CdGa₂S₄ crystal. It is found that the EPR spectra correspond to tetragonal symmetry. The spin Hamiltonian H = βB · g · S + B ₂ ⁰ O ₂ ⁰ + B ₄ ⁰ O ₄ ⁰ + B ₄ ⁴ O ₄ ⁴ with the parameters B ₂ ⁰ =23659±2 MHz, B ₄ ⁰ =1.9±1 MHz, |B ₄ ⁴ |=54.2±2 MHz, g_‖=1.93±0.02, and g_⊥=1.99±0.02 is used to describe the observed spectra. It is concluded that chromium ions occupy one of the tetrahedrally coordinated cation positions.     

Antiferromagnetic Resonance in GdB<Subscript>6</Subscript>

The electron spin resonance has been measured for the first time both in the paramagnetic phase of the metallic GdB₆ antiferromagnet (T_N = 15.5K) and in the antiferromagnetic state (T < T_N). In the paramagnetic phase below T* ~ 70 K, the material is found to exhibit a pronounced increase in the resonance linewidth and a shift in the g-factor, which is proportional to the linewidth Δg(T) ~ ΔH(T). Such behavior is not characteristic of antiferromagnetic metals and seems to be due to the effects related to displacements of Gd³⁺ ions from the centrosymmetric positions in the boron cage. The transition to the antiferromagnetic phase is accompanied by an abrupt change in the position of resonance (from μ₀H₀ ≈ 1.9 T to μ₀H₀ ≈ 3.9 T at ν = 60 GHz), after which a smooth evolution of the spectrum occurs, resulting eventually in the formation of the spectrum consisting of four resonance lines. The magnetic field dependence of the frequency of the resonant modes ω₀(H₀) obtained in the range of 28–69 GHz is well interpreted within the model of ESR in an antiferromagnet with the easy anisotropy axis ω/γ = (H ₀ ² +2H_AH_E)^1/2, where H_E is the exchange field and H_A is the anisotropy field. This provides an estimate for the anisotropy field, H_A ≈ 800 Oe. This value can result from the dipole?dipole interaction related to the mutual displacement of Gd³⁺ ions, which occurs at the antiferromagnetic transition.     

Acoustic emission and thermal expansion of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> and Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> crystals

The temperature dependence of the elongation per unit length for Pb(Mg_1/3Nb_2/3)O₃ crystals unannealed after growth and mechanical treatment is investigated in the course of thermocycling. It is revealed that this dependence deviates from linear behavior at temperatures below 350°C. The observed deviation is characteristic of relaxors, is very small in the first cycle, increases with increasing number n of thermocycles, and reaches saturation at n≥3. In the first cycle, a narrow maximum of the acoustic emission activity is observed in the vicinity of 350°C. In the course of thermocycling, the intensity of this maximum decreases and becomes zero at n>3. For (1?x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ crystals, the dependence of the temperature of this acoustic emission maximum on x exhibits a minimum. It is assumed that the phenomena observed are associated with the phase strain hardening due to local phase transitions occurring in compositionally ordered and polar nanoregions.     

Spectroscopy of NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Tm<Superscript>3+</Superscript> and NaGd(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Tm<Superscript>3+</Superscript> crystals as advanced laser materials

Single crystals of double sodium-containing lanthanum and gadolinium molybdates doped with Tm³⁺ ions were synthesized by the Czochralski method. The spectroscopic properties of these crystals were investigated from the viewpoint of their use as active media in diode-pumped lasers. The polarized spectra of absorption on the ³ H ₄ and ³ F ₄ levels and the polarized spectra of luminescence due to the ³ F ₄-³ H ₆ laser transition were recorded, and the lifetimes of the ³ H ₄ and ³ F ₄ excited states of the Tm³⁺ ions were determined. The luminescence cross sections were calculated using the Füchtbauer-Ladenburg formula. The simulation of the decay curve of the ³ H ₄ excited state according to the Golubov-Konobeev-Sakun method revealed that, in the crystals under investigation, the interaction between Tm³⁺ ions predominantly occurs through the dipole-dipole mechanism.     

Electrospun Dy-doped SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript> nanofibers: microstructure and magnetic properties

SrDy _x Fe_12?x O₁₉ (x ≤ 0.08) nanofibers have been synthesized by the electrospinning method followed by calcinations process. The partial substitution of rare earth ions Dy³⁺ (10.5 μ _B of magnetic moments) mainly occupying 12k sublattice sites in the SrFe₁₂O₁₉ crystal structure is investigated and discussed in this work. An enhanced coercivity of 7155 Oe has been obtained when the doped content reached to 0.08 at a relative low calcination temperature of 800 °C. As a result, we believe the synthesized SrDy _x Fe_12?x O₁₉ nanofibers can potentially be useful in high-density recording media as well as permanent magnets.     

Elastic properties of La<Subscript>0.82</Subscript>Ca<Subscript>0.18</Subscript>MnO<Subscript>3</Subscript> single crystal

The temperature dependences of the velocity of longitudinal sound waves and the internal friction in a La_0.82Ca_0.18MnO₃ single crystal with the Curie temperature T _C = 181 K have been studied. As temperature decreases, the single crystal is shown to undergo the transition from the pseudocubic O* to the Jahn–Teller O’ phase at T ~ 254 K and the reverse transition from O’ to O* phase at T ~ 84 K. The velocity of sound and the internal friction in the O’ phase are found to be significantly smaller than those in the O* phase.     

Nonstoichiometric high-pressure phase of Tm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

Tm _x Cu₃V₄O₁₂, a perovskite-like oxide (space group, Im-3; Z = 2; a = 7.279–7.293 Å) containing vacancies in its cationic sublattice, was obtained barothermally (P = 7.0–9.0 GPa, t = 1000–1100°C) for the first time. The temperature dependences on the electrical resistivity (10–300 K) and the magnetic susceptibility (0–300 K) were investigated. It was shown that the oxide Tm _x Cu₃V₄O₁₂ is characterized by metal-type conductivity and paramagnetic properties.     

Ionic displacements and structure of disordered PbFe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript>

A sequence of structural models of unit cells of complex oxides with perovskite-type structure has been constructed to refine the average structure of PbFe_1/2Nb_1/2O₃ (PFN) at temperatures above the ferroelectric Curie point (T _C ～ 110°C). Owing to the analysis of the probability theory considerations, each model is characterized by only two positional fitting parameters. With the use of the intensities of 95 symmetrically independent X-ray reflections from a PFN single crystal at 160°C, a model with the R factor below 3% (K = 2.44%) was chosen. The ravine method has been used to verify the existence of a single minimum for the R factor with respect to the fitting parameter.     

An Electron Paramagnetic Resonance Study of the Orbital Ordering Compound MgTi<Subscript>2</Subscript>O<Subscript>4</Subscript>

We report the electron paramagnetic resonance (EPR) studies of MgTi₂O₄ in the 300–140 K range. Above the transition temperature T _t (~258 K), the EPR results indicate that MgTi₂O₄ is paramagnetic. The parameters of the EPR spectra show an anomalous change at T _t. The clear EPR lines can be observed in temperature between T _t and 220 K. Besides that the EPR intensity, g value, and EPR linewidth increase with decreasing temperature; in temperature range below 220 K, no clear EPR line can be detected. The EPR spectra results demonstrate that magnetic spin-singlet state and the orbital density wave of MgTi₂O₄ system are formed gradually with decreasing temperature at low temperature range.     

Microwave dielectric properties of Ba(Zn<Subscript>1/3</Subscript>Ta<Subscript>2 / 3</Subscript>)O<Subscript>3</Subscript> for application in high power waveguide window

Higher dielectric constant, low dielectric loss and good transmission characteristicshave been the goal for developing the ceramic waveguide window for high power windowapplications. The choice of materials having high k with low dielectric lossand reduced window size is key parameters to achieve maximum microwave transmissionwithout unleashing microwave dissipation. The microwave dielectric properties ofsynthesized Ba(Zn_1/3Ta_{2 /3})O₃ (BZT) ceramics have been studied for high power windowapplications. The structural studies are correlated with microwave dielectric propertiesof BZT. The maximum values of dielectric constant ?_r =30, Q ×f₀ = 102 THz and near zero temperaturecoefficient of resonance frequency were obtained for BZT ceramics sintered at thetemperature of 1550 °Cfor 4 h. The measured results are used to design a tapered transition from air filledwaveguide to narrow (reduced width and height) dielectric filled waveguide using Heckenslinear taper at a specific frequency. The simulation result shows that the lowerreflection loss is obtained for the tapered transition of the narrow BZT window ascompared to the standard waveguide BZT window. The return loss of –34 dB is obtained forS-bandwaveguide window with a bandwidth of 675 MHz. The return loss observed in the narrow BZTwindow is –46 dB with a bandwidth of 570 MHz at a center frequency of 3.63 GHz. Most ofthe disadvantages in conventional windows will be rectified using the design of the tapertransion employing narrow waveguide window in high power applications.     

In-plane torque and gap symmetry of untwinned YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7</Subscript> crystals

The reversible magnetic torque of untwinned YBa₂Cu₃O₇ single crystals shows the four-fold symmetry in thea-b plane. The irreversible torque indicates evidence for a novel intrinsic pinning along thea andb axes. These facts mean that the free energy of the four-fold symmetry has a minimum when the field is applied along thea orb axis. The results are consistent with those expected from thed _x ²?y ² symmetry and rule out the possibility of thed _xy symmetry. The Fermi surface anisotropy is not responsible for the observed anisotropy. This is firstbulk evidence for thek-dependent gap anisotropy on the Fermi surface. The two-fold anisotropy parameter is found as\(\gamma _{ab} = \sqrt {{{m_a } \mathord{\left/ {\vphantom {{m_a } {m_b }}} \right. \kern-\nulldelimiterspace} {m_b }}} = 1.18 \pm 0.14\).     

The magnetization reversal in CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/CoFe<Subscript>2</Subscript> granular systems

The temperature-dependent field cooling (FC) and zero-field cooling (ZFC) magnetizations, i.e., M _FC and M _ZFC, measured under different magnetic fields from 500 Oe to 20 kOe have been investigated on two exchange–spring CoFe₂O₄/CoFe₂ composites with different relative content of CoFe₂. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at a field-dependent irreversible temperature T _irr. For the sample with less CoFe₂, the curves of ?d(M _FC ? M _ZFC)/dT versus temperature T exhibit a broad peak at an intermediate temperature T ₂ below T _irr , and the moments are suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the ?d(M _FC ? M _ZFC)/dT curves of the sample with more CoFe₂, besides a broad peat at an intermediate temperature T ₂, a rapid rise around the low temperature T ₁~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T ₂ and T _irr towards a lower temperature, and the shift of T ₂ is attributable to the moment reversal of CoFe₂O₄.

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Graphical abstract CoFe₂O₄/CoFe₂ composites with different relative content of CoFe₂ were prepared by reducing CoFe₂O₄ in H₂ for 4 h (S4H) and 8 h (S8H). The temperature-dependent FC and ZFC magnetizations, i.e., M _FC and M _ZFC, under different magnetic fields from 500 Oe to 20 kOe have been investigated. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at field-dependent irreversible temperature T _irr. For the S4H sample, the curves of ?d(M _FC ? M _ZFC)/dT versus temperature T exhibit a broad and field-dependent relaxing peak at T ₂ below T _irr (figure a), and the moments were suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the S8H sample, it exhibits the reentrant spin-glass state around 50 K, as evidenced by a peak in the M _FC curve (inset in figure b) and as a result of the cooperative effects of the random anisotropy of CoFe₂O₄, exchange–spring occurring at the interface of CoFe₂O₄ and CoFe₂ together with the inter-particle dipolar interaction (figure c); in ?d(M _FC ? M _ZFC)/dT curves, besides a broad relaxing peat at T ₂, a rapid rise around the low-temperature T ₁~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T ₂ and T _irr towards a lower temperature, and the shift of T ₂ is attributable to the moment reversal of CoFe₂O₄.

     

Optical properties and mechanisms of current flow in Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> films prepared by spray pyrolysis

Thin films Cu₂ZnSnS₄ (up to 0.9 μm thick) with p-type conductivity and band gap E_g = 1.54 eV have been prepared by the spray pyrolysis of 0.1 M aqueous solutions of the salts CuCl₂ · 2H₂O, ZnCl₂ · 2H₂O, SnCl₄ · 5H₂O, and (NH₂)₂CS at a temperature T_S = 290°C. The electrophysical properties of the films have been analyzed using the model for polycrystalline materials with electrically active grain boundaries. The energy and geometric parameters of the grain boundaries have been determined as follows: the height of the barriers is E_b ≈ 0.045–0.048 eV, and the thickness of the depletion region is δ ≈ 3.25 nm. The effective concentrations of charge carriers p₀ = 3.16 × 10¹⁸ cm^–3 and their mobilities in crystallites μ_p = 85 cm²/(V s) have been found using the technique for determining the kinetic parameters from the absorption spectra of thin films at a photon energy hν ≈ E_g. The density of states at grain boundaries N_t = 9.57 × 10¹¹ cm^–2 has been estimated.