Single crystal polarized Raman spectra of the solid electrolyte Cu2HgI4; attempt frequencies for ion motion in Ag2HgI4

The polarized Raman scattering from small single crystals of Cu₂HgI₄ provided assignments for the more prominent Raman features to specific irreducible representations. The E symmetry assignment, mass dependence, and pressure dependence of the 36 cm^?1 band in Cu₂HgI₄ and 24 cm^?1 band in Ag₂HgI₄ indicate that these features approximate the attempt frequency for ion hopping. The unusually high pre-exponential factor in the Arrhenius expression for ion hopping is discussed in light of the observed attempt frequency; we conclude that despite the high activation energy the conduction mechanism is similar to other heavy-metal solid electrolytes.     

Pressure dependence of transport and optical properties of Ag2HgI4

Silver mercury iodide, Ag₂HgI₄, has been studied to pressures of 75–100 kbar at 25°C. There are now four high pressure phases known. Transport studies indicate predominantly electronic conduction, with the highest pressure phase showing rectification in an asymmetric conductivity cell. Optical studies now corroborate the four high pressure phases. For two of the phases the energy gap shifts to lower energies with increasing pressure.     

Electrical conductivity and composition range of Ag2HgI4 between room temperature and 75°C

The composition range of α- and β-Ag₂HgI₄ near the transformation temperature is determined by X-ray diffraction. The electrical conductivity measured in the α-phase is nearly unaffected by deviation from stoichiometry. This is caused by a compensation of the composition dependences of σ₀ and of the activation energy E_A. From the experimental results the dependences of the entropy and of the Gibbs energy for migration of Ag-ions on temperature and on composition are estimated.     

Hot stage X-ray diffractometer studies on Ag2PbI4 and Ag4PbI6

Mixtures of AgI and PbI₂ cooled from the melt result in the peritectic formation of a fast ion conducting phase centred about Ag₄PbI₆, which is face centred cubic with a = 6.33(5)A; this phase exhibits high electrical conductivity. On cooling to about 125°C, dissociation occurs to γAgI and PbI₂, accompanied by the transient formation of another phase, centred about Ag₂PbI₄. A modified form of the T-x section of the equilibrium phase diagram at AgI concentrations greater than 60 mole % and below 300°C is proposed.     

Magnetic properties for the Cu2MnSnSe4 and Cu2FeSnSe4 compounds

Magnetic susceptibility χ measurements in the range from 2 to 300 K were carried out on samples of the Cu₂FeSnSe₄ and Cu₂MnSnSe₄ compounds. It was found that Cu₂FeSnSe₄ was antiferromagnetic showing ideal Curie-Weiss behavior with a Néel temperature T_N of about 19 K and Curie-Weiss temperature θ=−200 K, while for Cu₂MnSnSe₄ the behavior was spin-glass with a freezing temperature T_f of about 22 K and Curie-Weiss temperature θ=−25 K. The spin-glass order parameter q(T), determined from the susceptibility data, was found to be in agreement with the prediction of conventional spin-glass theory.     

X-ray investigations of modulations in Cs2ZnI4

The X-ray diffractometer patterns of a reciprocal space have been analyzed in the modulated phases of Cs₂ZnI₄ crystals. The character of the atomic displacements in the modulation wave has been established. The temperature behaviour of both a modulation wave vector and amplitude has been determined from the position and intensity of satellite reflections.     

Pressure induced resonance of the Raman linewidth of the A1 mode of Cu3V S4

Investigations of the Raman spectrum of Cu₃V S₄ under pressure up to 60 kbar show a pronounced enhancement of the linewidth of the A₁ mode around 20 kbar. This anomaly is interpreted in terms of a resonance between the A₁ mode and a double phonon structure arising from the combination of F₂ like zone center phonons.     

Theoretical studies on the structural, electronic, and optical properties of Ag2HgSnSe4

We investigate the electronic structure of Ag₂HgSnSe₄ in a wurtzite-stannite structure with the first principles method. This crystal is a direct band-gap compound. In addition the dielectric function, absorption coefficient, reflectivity, and energy-loss function are studied using the density functional theory in the generalized gradient approximation. We discuss the optical transitions between the valence bands and the conduction bands in the spectrum of the imaginary part of the dielectric function at length. We also find a very high absorption coefficient and a wide absorption band for this material. The prominent structures in the spectra of reflectivity and the energy-loss function are discussed in detail.     

X-ray diffraction, Raman spectrum and magnetic susceptibility of the magnetic semiconductor Cu2FeSnS4

In an attempt to resolve the crystal structure and the corresponding space group of the magnetic semiconductor Cu₂FeSnS₄, samples of this compound were studied by X-ray diffraction, differential thermal analysis, Raman scattering and magnetic susceptibility. It was found that at room temperature this compound prepared by a careful crystal growth process, including annealing to equilibrium at a suitable temperature followed by slow cooling of the samples to 300 K, crystallizes in a tetragonal structure with space group .     

Theoretical studies on the structural, electronic, and optical properties of Cu2CdGeSe4

We investigate the electronic structure for Cu₂CdGeSe₄ in stannite structure with the first-principles method. This crystal is the direct band gap compound. In addition, the dielectric function, absorption coefficient, reflectivity, and energy-loss function are studied using the density functional theory within the generalized gradient approximation. We discuss the optical transitions between the valence bands and the conduction bands in the spectra of the imaginary part of the dielectric function at length. We also find a very high absorption coefficient and wide absorption spectrum for this material. The prominent structures in the spectra of reflectivity and energy-loss function are discussed in detail.     

Magnetic behaviour of Cu2FeGeSe4

Measurements of magnetic susceptibility χ as a function of temperature T and of magnetisation M as a function of applied magnetic field H at a number of fixed temperatures were made on polycrystalline samples of Cu₂FeGeSe₄. The χ versus T data show that an antiferromagnetic transition occurs at 20 K and that a second transition occurs at 8 K, indicating a transition to weak ferromagnetic form. The M versus H curves indicated that at all temperatures below 70 K bound magnetic polarons (BMP) occur, in the paramagnetic, antiferromagnetic and weak ferromagnetic ranges. Below 8 K, the M versus H curves exhibited magnetic hysteresis, and this is attributed to the interaction of the BMPs with tetragonally anisotropic matrix. The B versus H curves were well fitted by a Langevin-type of equation, and the variation of the fitting parameters determined as a function of temperature. These showed that above 20 K the total BMP magnetisation fell almost linearly with increasing temperature and effectively disappeared at 70 K. The number of BMPs remained practically constant with temperature having a mean value of 6.55×10¹⁸/cm³. The analysis gave a value of 213 μ_B for the average magnetic moment of a BMP, corresponding to 42.4 Fe atoms. Using a simple spherical model, this gives the radius of a BMP as 12.0 Å.     

Raman spectra of the orthorhombic semiconductor compound Cu2SnTe3

The optical phonon spectrum of the semiconductor Cu₂SnTe₃, that crystallizes in the orthorhombic structure with space group Imm2 (), have been studied by measuring unpolarized Raman scattering between 10 and 300 K. The experimental frequencies of the phonon modes observed were compared to those calculated by using simplified lattice dynamical models reported in the literature. From combined analysis of these results together with the factor group analysis of the zone-center vibrational modes, valuable information about these modes was obtained and their possible symmetry was assigned. A₁ modes at 71, 123, 167, 176 and 190 cm⁻¹; A₂ modes 115 and 131 cm⁻¹; B₁ modes at 76, 142 and 152 cm⁻¹; B₂ modes at 89, 100 and 206 cm⁻¹; a overtone at 246 cm⁻¹, and combinations at 218, 270 and 292 cm⁻¹; have been observed in this compound.     

Physical studies on composites Ag7I4VO4-Al2O3

The electrical properties of the solid electrolytes Ag₇I₄VO₄-Al₂O₃ (0-40 mol% Al₂O₃) are investigated. The electrical conductivity, dielectric constant and dielectric loss are increased by increasing the concentration of Al₂O₃; showing a maximum at 30 mol% Al₂O₃. The conductivity is found to be increased by decreasing the particle size of Al₂O₃. The results are explained using the random resistor network model (RRN). This is due to the formation of a highly conducting interface layer along the matrix-particle interface. This layer is destroyed at concentrations higher than 30 mol% Al₂O₃.     

Ab initio band structure calculations of the low-temperature phases of Ag2Se, Ag2Te and Ag3AuSe2

Ab initio band structure calculations were performed for the low-temperature modifications of the silver chalcogenides β-Ag₂Se, β-Ag₂Te and the ternary compound β-Ag₃AuSe₂ by the local spherical wave (LSW) method. Coordinates of the atoms of β-Ag₂Se and β-Ag₃AuSe₂ were obtained from refinements using X-ray powder data. The structures are characterized by three, four and five coordinations of silver by the chalcogen, a linear coordination of gold by Se, and by metal-metal distances only slightly larger than in the metals. The band structure calculations show that β-Ag₃AuSe₂ is a semiconductor, while β-Ag₂Se and β-Ag₂Te are semimetals with an overlap of about 0.1-0.2 eV. The Ag 4d and Au 5d states are strongly hybridized with the chalcogen p states all over the valence bands. β-Ag₂Se and β-Ag₂Te have a very low DOS in the energy range from about −0.1 to +0.5 eV. The calculated effective mass β-Ag₂Se is about 0.1-0.3 m_e for electrons and 0.75 m_e for holes, respectively.     

Dynamics and crystal chemistry of tellurites: 1. Raman spectra of thallium tellurites: Tl2TeO3, Tl2Te2O5 and Tl2Te3O7

Raman spectra of the three entitled crystals are analysed within the framework of a lattice-dynamical model treatment using preliminary obtained X-ray diffraction data. The short range atomic arrangement and spectrochemical peculiarities of these structures are jointly discussed, which is considered as an initial step for studying the nature of the glass phases in the xTl₂O+(1−x)TeO₂ system. The charged TeO₃²⁻ groups and the neutral TeO₂ quasi-molecules are proposed as the basic units forming the complex tellurite anions. However, no relevant characteristic frequencies can be indicated in the spectra since the interatomic separation in those units are highly variables and their vibrational states are mixed and delocalised.     

Photoelectronic and electrical properties of Tl2InGaS4 layered crystals

Tl₂InGaS₄ layered crystals are studied through the dark electrical conductivity, space charge limited current and illumination- and temperature-dependent photoconductivity measurements in the temperature regions of 220-350 K, 300-400 K and 200-350 K, respectively. The space charge limited current measurements revealed the existence of a single discrete trapping level located at 0.44 eV. The dark electrical conductivity showed the existence of two energy levels of 0.32 eV and 0.60 eV being dominant above and below 300 K, respectively. The photoconductivity measurements reflected the existence of two other energy levels located at 0.28 eV and 0.19 eV at high and low temperatures, respectively. The photocurrent is observed to increase with increasing temperature up to a maximum temperature of 330 K. The illumination dependence of photoconductivity is found to exhibit supralinear recombination in all the studied temperature ranges. The change in recombination mechanism is attributed to exchange in the behavior of sensitizing and recombination centers.     

NMR and magnetic studies on 7 K anomaly in Tl3H(SO4)2

Measurements of the spin-lattice relaxation time, NMR absorption line and magnetization have been carried out on the Tl₃H(SO₄)₂ crystal below 50 K. The anomaly at around 7 K was: (1) the spin-lattice relaxation times of ¹H and ²⁰⁵Tl nuclei increase steeply with decreasing temperature below 7 K, (2) the NMR absorption lines below 7 K shift to the high-magnetic field side in comparison with that above 7 K, and (3) the ¹H NMR line width exhibits a drastic increase of the line width with decreasing temperature below 7 K. These results indicate that the magnetic dipole fluctuation of the proton changes at 7 K. On the other hand, there are no remarkable anomalies of magnetic susceptibility at around 7 K. From these results it is deduced that the anomaly at around 7 K is caused by the change in quantum mechanical process of the proton from proton tunneling to zero-point vibration of hydrogen in the hydrogen bond with the decrease of temperature.     

Preparation, characterization and oxide ion conductivity in U-substituted Bi4V2O11

A Bi₂V_{1 − x − y}U_xBi_yO_{5.5 + 0.5x − y} solid solution derived from Bi₄V₂O₁₁ has been prepared and characterized with x up to 0.125 for y = 0. Partial substitution of U⁶⁺ for V⁵⁺ in Bi₄V₂O₁₁ leads to the stabilization at room temperature of the high-oxide ion conducting γ-phase, in contrast with other M⁶⁺ dopants which stabilize the β-phase. The lower conductivity in U substituted system compared with BICUVOX.10 is attributed to its higher activation energy. Conductivity values and activation energies of the U substituted phases compare well with Bi₂UO₆.     

Pressure dependence of superconductivity in the pseudo-one-dimensional compound Tl2Mo6Se6

Measurements of the temperature and pressure dependences of the resistivity of the pseudo-one-dimensional ternary compound Tl₂Mo₆Se₆ are presented. We find that the conductivity parallel to the highly conducting c-axis is enhanced by pressure and the superconducting transition temperature T_c is suppressed by pressure at a rate $\text{?T}{}_{\mathrm{c}}\text{?P}\text{=?7.6×10}{}^{\mathrm{?5}}$ kbar^?1. These results are discussed in relation to the current models of transport in one-dimensional conductors.