Influence of crystal synthesis on the incommensurate phase and lock-in transition of Rb2ZnCl4 crystals

A comparative study of several crystals of Rb₂ZnCl₄, obtained by different crystal growing methods, has allowed us to determine the influence of growth defects on the incommensurate phase and on the lock-in transition of these samples. X-ray diffraction has allowed us to complete previous dielectric measurements realized on the same samples and to relate the crystalline quality to the evolution of the modulation as a function of the temperature. The principal influence of an increasing defect density seems to be a stronger pinning of the modulated phase and this induces a lower lock-in temperature and a wider hysteresis.     

Commensurate and incommensurate modulated structures of Rb2ZnCl4

The commensurate and incommensurate structures of Rb₂ZnCl₄ have been refined using the four-dimensional formalism for modulated structures. They are characterized by a rigid body modulated rotation of the ZnCl₄ tetrahedra and by a translation motion of the Rb atoms.     

Atomic 6p-Tl0 centers in ferroelectric Rb2ZnCl4 crystals

Abstract

Several Tl⁰ (6s²6p ¹)-type paramagnetic centers, produced by low temperature X-ray irradiation, were observed and studied by electron spin resonance (ESR) in the orthorhombic ferroelectric phase of thallium doped Rb₂ZnCl₄ crystals. The centers were formed by electron trapping at Tl⁺ ions localized substitutionally at Rb⁺ sites. The number and properties of the observed centers account for the tripling of the unit cell in the ferroelectric phase.     

Synthesis, electrical and dielectric properties of FeVO4 nanoparticles

The electrical and dielectric properties of FeVO₄ nanoparticles were studied at different temperatures from ambient to 200 °C. The samples were prepared by simple co-precipitation method using ferric nitrate and ammonium metavanadate as the starting precursors. The powder X-ray diffraction pattern inferred the single phase formation and triclinic structure of FeVO₄. The morphology of the particles was elucidated from SEM studies. Detailed studies on the electrical and dielectric properties of the compound were carried out by using solid state impedance spectroscopy. A maximum dc conductivity of 4.65×10⁻⁵ S cm⁻¹ was observed at the measuring temperature of 200 °C. The calculated activation energy from dc conductivity was found to be 0.28 eV. It was evident that the electrical transport process in the system was due to the hopping mechanism. The detailed dielectric studies were also carried out.     

Dielectric properties of [N(CH3)4]2ZnCl4 crystal under influence of electric field and uniaxial stresses

Abstract

Dielectric and light scattering spectroscopy are the most sensitive methods for the direct observation of low-frequency excitations in incommensurate phases. In several cases they have been successfully used for the observation of amplitudon and phason modqs. Whereas the amplitudon below the normal-incommensurate transition temperature behaves in a similar way to soft modes at common structural transitions, the phason represents a qualitatively new feature of incommensurate phases. All the corresponding experimental data published up to the middle of 1980 are reviewed and consistently interpreted taking into account the specific selection rules recenily derived. The necessary theoretical background is discussed qualitatively.     

Analysis of the ferroelastic domains and phase transition in the K2SO4 crystal

Abstract

The domain structures of the β-K₂SO₄ crystal were analyzed by group theory. We obtained the permissible kinds of domain association and domain walls from the results of the group theory. It is suggested from the analysis that the (110) and (130) planes are W_mb walls. The value of the spontaneous strain of K₂SO₄ wast = 6.32 × 10^?3 at room temperature and also its temperature dependence was observed.     

Linear birefringence studies of incommensurate systems: II. KFeF4

Abstract

The temperature dependence of the linear birefringence (LB), Δn _c , is measured in the range 5 K ? T ? 500 K on samples of KFeF₄, which originate from hydrothermal, flux and Bridgman growth techniques. Pronounced anomalies are found at the orthorhombic-orthorhomic phase transition at T _c ∽ 400 K. It is weakly discontinuous with a near-tricritical exponent β ∽ 0.2. Weak anomalies near T _i ∽ T _c + (25 … 40 K) seem to indicate a transition into an intermediate incommensurate phase. Its XY-model character is reflected by the critical LB exponent β = 0.8 ± 0.1. A smooth LB anomaly below 200 K is due to 2-dimensional ferromagnetic spin-order.     

Mixed alkali metal selenate proton conductors: Phase transitions and crystal structure of [Rb0.54(Nh4)0.46]3H(SeO4)2

Optical birefringence, calorimetric, thermal expansion, powder and single crystal X-ray diffraction investigations of mixed proton conductors [Rb_1-x(NH₄)_x]₃H(SeO₄)₂ were performed with the aim of studying the influence of partial substitution of cations on the superprotonic phase transition, on the atomic structure and on other characteristic features of this type of crystals.     

The interface structure of nano-SiO2/PA66 composites and its influence on material's mechanical and thermal properties

The PA66-based nanocomposites containing surface-modified nano-SiO₂ were prepared by melt compounding. The interface structure formed in composite system was investigated by thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The influence of interface structure on material's mechanical and thermal properties was also studied. The results indicated that the PA66 chains were attached to the surface of modified-silica nanoparticles by chemical bonding and physical absorption mode, accompanying the formation of the composites network structure. With the addition of modified silica, the strength and stiffness of composites were all reinforced: the observed increase depended on the formation of the interface structure based on hydrogen bonding and covalent bonding. Furthermore, the differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) showed that the presence of modified silica could affect the crystallization behavior of the PA66 matrix and lead to glass transition temperature of composites a shift to higher temperature.     

X-ray study of the low-temperature phase transition in K2CoCl4

Precise lattice parameter measurements and intensity measurements of selected main and satellite reflections of K₂CoCl₄ have been performed in the temperature range 100 to 300 K in the vicinity of the low-temperature phase transition (commensurate-commensurate phase transition, T _c = 142 K). A broadening of the FWHM for the h01 reflections was observed below 142 K which suggests a transition from an orthorhombic phase to a monoclinic phase.     

DSC study of superionic phase transition in (NH4)4H2(SeO4)3 single crystals

DSC and complex impedance studies of the protonic conductor (NH₄)₄H₂(SeO₄)₃, which undergoes a superionic phase transition of first order at T_s = 378 K show that the activation energy of ionic conductivity d(lg σ)/dt and the ordering enthalpy ΔC_p of the crystal are proportional: d(lg σ)/dT = XΔC_p/RT_s + const, as found for MAg₄I₅ crystals undergoing a second-order superionic phase transition. Thus the short-range order environment of the species involved in fast-ion transport plays the main role in the superionic phase transition. This is also supported by the value of the entropy change at T_s, ΔS = 43 J/mole·K. A new metastable phase was found to be induced on heating the (NH₄)₄H₂(SeO₄)₃ crystal above T_s.     

Investigations of elastic properties at very low frequencies: Method and behaviour of (TMA)2ZnCl4

Abstract

A new apparatus to perform longitudinal elastic strain measurements over a frequency range from 10^?4 Hz to 10¹ Hz is presented. First results of measurements on TMAZC with the prototype of this device are given. These results will be discussed in connection with the new methods.     

Structure formation and mechanisms of DC conduction in thermally evaporated nanocrystallite structure ZnIn2Se4 thin films

ZnIn₂Se₄ is of polycrystalline structure in as synthesized condition. It transforms to nanocrystallite structure of ZnIn₂Se₄ film upon thermal evaporation. Annealing temperatures influenced crystallite size, dislocation density and internal strain. The hot probe test showed that ZnIn₂Se₄ thin films are n-type semiconductor. The dark electrical resistivity versus reciprocal temperature for planar structure of Au/ZnIn₂Se₄/Au showed existence of two operating conduction mechanisms depending on temperature. At temperatures >365 K, intrinsic conduction operates with activation energy of 0.837 eV. At temperatures <365 K, extrinsic conduction takes place with activation energy of 0.18 eV. The operating conduction mechanism in extrinsic region is variable range hopping. The parameters such as density of states at Fermi level, hopping distance and average hopping energy have been determined and it was found that they depend on film thickness. The dark current–voltage characteristics of Au/n-ZnIn₂Se₄/p-Si/Al diode at different temperatures ranging from 293–353 K have been investigated. Results showed rectification behavior. At forward bias potential <0.2 V, thermionic emission of electrons from ZnIn₂Se₄ film over a potential barrier of 0.28 V takes place. At forward bias potential >0.2 V, single trap space charge limited current is operating. The trap concentration and trap energy level have been determined as 3.12×10¹⁹ cm⁻³ and 0.24 eV, respectively.     

Anisotropic transport and optical properties of superconducting (La1-xSrx)2CuO4 single crystal thin films

An experimental study on the resistivity, Hall coefficient, upper critical field, and optical reflection and transmission characteristics is described for single-crystalline superconducting (La_1-xSr_x)₂CuO₄ thin films epitaxially grown on SrTiO₃ single crystal substrates by rf magnetron sputtering. These properties exhibit pronounced anisotropy between the c-axis direction and the Cu-O plane. The characteristics are consistently explained from the point of view of the two-diemensional (2D) electronic structure. The most noteworthy implication of the experimental results is that the transport along the c-axis is far from an itinerant picture. This leads to the idea that the superconductivity in the series of cuprate materials is caused by the 2D electronic system arising from the Cu-O planes, and some interactions between them, which is not possibly due to itinerant carriers.     

Investigation of the optoelectronic properties of columbite ZnNb2O6 crystal

A high-quality ZnNb₂O₆ single-crystal grown by optical floating zone method has been used as a research prototype to analyze the optoelectronic parameters by measuring the absorption coefficient and transmittance spectra along the b-axis from 200 nm to 1000 nm at room temperature. The optical interband transitions of ZnNb₂O₆ have been determined as a direct transition with a band gap of 3.84 eV. The refractive index, extinction coefficient, and real and imaginary parts of the complex dielectric constants as functions of the wavelength for ZnNb₂O₆ crystal are obtained from the measured absorption coefficients and transmittance spectra. In the Urbach tail of 3.16–3.60 eV, the validity of the Cauchy–Sellmeier equation has also been evaluated. Using the single effective oscillator model, the oscillator energy E_o is found to be 4.77 eV. The dispersion energy E_d is 26.88 eV and ZnNb₂O₆ crystal takes an ionic value.     

Infrared active phonon modes and ionicity of single crystal MgAl2O4

Near-normal incident infrared reflectivity spectra of （100） MgAl2O4 spinel single crystal have been measured at different temperatures in the frequency region between 50 and 6000 cm^-1. Eight infrared-active phonon modes are identified, which are fitted with the factorized form of the dielectric function. The dielectric property and optical conductivity of the MgAl2O4 crystal are analysed. From TO/LO splitting, the effective Szigeti charges and Born effective charges at different temperatures are calculated for studying the ionicity and the effect of polarization. Based on the relationship between the （LO-TO）1 splitting, which represents the transverse and longitudinal frequencies splitting of the highest energy phonon band in the reflectivity spectrum, and the ionic-covalent parameter, the four main phonon modes are assigned. MgA1204 can be considered as a pure ionic crystal and its optical characters do not change with decreasing temperature, so it may be used as a suitable substrate for high-Tc superconducting thin films.     

Magnetic and dielectric properties of alkaline earth Ca and Ba ions co-doped BiFeO3 nanoparticles

Ca²⁺ and Ba²⁺ ions co-doped BiFeO₃ nanoparticles, Bi_0.8Ca_0.2−xBa_xFeO₃ (x=0-0.20), were prepared by a sol-gel method. The phase structure, grain size, dielectric and magnetic properties of the prepared samples were investigated. The results showed that the lattice structure of the nanoparticles transformed from rhombohedral (x=0) to orthorhombic (x=0.07-0.19) and then to tetragonal (x=0.20) with x increased. The dielectric properties of the nanoparticles were affected by the properties of the substitutional ions as well as the crystalline structure of the samples. The magnetic properties of the nanoparticles were greatly improved and the T_N of the nanoparticles was obviously increased. All the Ca²⁺ and Ba²⁺ ions co-doped BiFeO₃ nanoparticles presented the high ratio of M_r/M from 0.527 to 0.571 and large coercivity from 4.335 to 5.163 KOe.     

A nuclear magnetic resonance study of the structural properties and molecular motions of Li2KH(SO4)2 and LiKSO4 single crystals

The structural properties and relaxation mechanisms of Li₂KH(SO₄)₂ crystals were determined using the temperature dependences of NMR spectra and the spin-lattice relaxation times (T₁) of their ¹H, ⁷Li, and ³⁹K nuclei. The results obtained were compared with the previously reported physical properties of LiKSO₄ crystals. The substitution of the potassium ions with protons in the LiKSO₄ crystals were variations in the phase transition temperatures, and the non-appearance of ferroelastic properties. The ⁷Li T₁ for the Li₂KH(SO₄)₂ crystals was much shorter than the ⁷Li T₁ for the LiKSO₄ crystals, and these findings indicate that the presence of the protons in Li₂KH(SO₄)₂ causes the Li ions to move with greater freedom.     

Optical study of the phase transitions in LiKSO4

The birefringence of LiKSO₄ has been measured over the range 27–700°C. The change in birefringence with heating and cooling is seen to be very different. Observations have been made on domains in (001) and (100) plates near the phase transitions.     

A low-temperature tilter system and its application to the measurement of the anisotropy of optical rotation in K2Zncl4 in the vicinity of the phase transition at 145 k

The ferroelectric/ferroelastic phase transition of K₂ZnCl₄ at 145 K has been investigated employing the tilter method (Kaminsky and Glazer (1996) Ferroelectrics 183, 133) which was adapted to low-temperature experiments. We were able to observe the anisotropy of optical rotation in K₂ZnCl₄ which shows a distinct discontinuity at the transition temperature. A precursor-optical rotation in the ferroelectric phase is discussed in connection with a cluster ordering scheme suggested in an earlier X-ray study. The rotation of the optical indicatrix which accompanies the transition from the orthorhombic to the monoclinic system shows a Landau-type temperature dependence. Model calculations based on the dipole-dipole interaction between the atoms of the structures at different temperatures are in qualitative agreement with the experimental results.