Dielectric properties and phase transitions in crystals of TlInS x Se2 − x solid solutions

This paper reports on a study of the dielectric permittivity and electrical conductivity of single-crystal TlInS _x Se_{2 − x} solid solutions as functions of temperature and composition. It has been found that the dielectric permittivity ɛ and electrical conductivity σ decrease with increasing x and increase with growing temperature. The temperature dependences ɛ = f(T) and σ = f(T) for TlInS _x Se_{2 − x} crystals have been demonstrated to reveal anomalies in the form of maxima, which suggests that these crystals undergo phase transitions. The temperatures of the phase transitions increase with increasing x.     

Structural and electrical properties of pure and H<Subscript>2</Subscript>SO<Subscript>4</Subscript> doped (PVA)<Subscript>0.7</Subscript>(NaI)<Subscript>0.3</Subscript> solid polymer electrolyte

Solid polymer electrolytes (SPE) based on poly-(vinyl alcohol) (PVA)_0.7 and sodium iodide (NaI)_0.3 complexed with sulfuric acid (SA) at different concentrations were prepared using solution casting technique. The structural properties of these electrolyte films were examined by X-ray diffraction (XRD) studies. The XRD data revealed that sulfuric acid disrupt the semi-crystalline nature of (PVA)_0.7(NaI)_0.3 and convert it into an amorphous phase. The proton conductivity and impedance of the electrolyte were studied with changing sulfuric acid concentration from 0 to 5.1 mol/liter (M). The highest conductivity of (PVA)_0.7(NaI)_0.3 matrix at room temperature was 10⁻⁵ S cm⁻¹ and this increased to 10⁻³ S cm⁻¹ with doping by 5.1 M sulfuric acid. The electrical conductivity (σ) and dielectric permittivity (ε′) of the solid polymer electrolyte in frequency range (500 Hz–1 MHz) and temperature range (300–400) K were carried out. The electrolyte with the highest electrical conductivity was used in the fabrication of a sodium battery with the configuration Na/SPE/MnO₂. The fabricated cells give open circuit voltage of 3.34 V and have an internal resistance of 4.5 kΩ.     

Ion conduction and space-charge polarization processes in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The electrical properties of a lithium heptagermanate (Li₂Ge₇O₁₅) crystal have been studied in DC and AC measuring fields at temperatures from 500 to 700 K. In a DC field, a substantial decrease of electrical conductivity σ with time has been detected. On the basis of kinetic dependences σ(t), estimates of the charge carrier diffusion coefficient D have been obtained. In the frequency range 10¹–10⁵ Hz, the spectra of complex impedance ρ*(f) have been measured. The analysis of diagrams in the complex plane (ρ″–ρ′) has been performed within the equivalent circuit approach. It has been shown that, in the considered temperature and frequency intervals, the electrical properties of Li₂Ge₇O₁₅ crystals have been determined by the hopping conduction of interstitial lithium ions A _Li and accumulation of charge carriers near the blocking Pt electrodes.     

Effect of ionizing irradiation on the mechanism of current passage in TlInSe<Subscript>2</Subscript> single crystals

The temperature dependence of the electrical conductivity and current-voltage characteristics of γ-irradiated TlInSe₂ single crystals with an electrical resistivity of ∼10⁸ Ω cm have been investigated. It has been established that the anomalies of the conductivity observed in weak electric fields and at low dozes of irradiation are related to the decomposition of neutral complexes containing an interstitial cation atom. In strong electric fields, a thermal-field ionization of traps occurs. The main mechanism of radiation defect formation is the formation of complexes [V _In⁻In _i ⁺], [V _Se⁻Se _i ⁻], and others with the structural defects characteristic of unirradiated crystals. The activation energy, trap concentrations, and the potential well shape near the traps have been determined.     

Anomalous increase of the thermopower and thermoelectric figure of merit in Ga-doped <Emphasis Type="Italic">p</Emphasis>-(Bi<Subscript>0.5</Subscript>Sb<Subscript>0.5</Subscript>)<Subscript>2</Subscript>Te<Subscript>3</Subscript> single crystals

The effect of Ga doping on the temperature dependences (5 K ≤ T ≤ 300 K) of the Seebeck coefficient α, electrical conductivity σ, thermal conductivity coefficient κ, and thermoelectric figure of merit Z of p-(Bi_0.5Sb_0.5)₂Te₃ single crystals has been investigated. It has been shown that, upon Ga doping, the hole concentration decreases, the Seebeck coefficient increases, the electrical conductivity decreases, and the thermoelectric figure of merit increases. The observed variations in the Seebeck coefficient cannot be completely explained by the decrease in the hole concentration and indicate a noticeable variation in the density of states due to the Ga doping.     

Effect of gamma irradiation on the dielectric properties and electrical conductivity of the TlInS<Subscript>2</Subscript> single crystal

The effect of gamma irradiation on the dielectric properties and ac conductivity of a TlInS₂ single crystal with a layered structure has been investigated in the frequency range from 5 × 10⁴ to 3.5 × 10⁷Hz. It has been shown that gamma irradiation of the TlInS₂ single crystal with a dose of 10⁴–2.25 × 10⁶ rad leads to a considerable increase in the dielectric loss tangent tanδ, the real part ɛ′ and imaginary part ɛ″ of the complex permittivity, and the ac conductivity σ _ac across the layers. It has been established that, for all gamma irradiation doses, the TlInS₂ single crystal is characterized by the dielectric loss due to electrical conduction up to a frequency of 10⁷ Hz and by the relaxation loss at a higher frequency. Irradiation of the TlInS₂ single crystal results in an increase in the dispersion of tan δ, ɛ′, and ɛ″. It has been demonstrated that, as the gamma irradiation dose is accumulated in the TlInS₂ single crystal, the density of localized states near the Fermi level N _F increases (from 5.2 × 10¹⁸ to 1.9 × 10¹⁹ eV⁻¹ cm⁻³).     

Crystal growth,electrical and photophysical properties of Tl<Subscript>2</Subscript>S layered single crystals

The Tl₂S compound was prepared in a single crystal form using a special local technique, and the obtained crystals were analysed by X-ray diffraction. For the resultant crystals, the electrical properties (electrical conductivity and Hall effect) and steady-state photoconductivity were elucidated in this work. The electrical measurements extend from 170 to 430 K, where it was found that σ _⊥ = 8.82 × 10⁻⁵ Sm⁻¹ when current flow direction makes right angle to the cleavage plane of the crystals. In the same range of temperatures, it was found that σ _‖ = 4.73 × 10⁻⁵ Sm⁻¹ when the current flow is parallel to the cleavage plane. In line with the investigated range of temperatures, the widths of the band gaps were calculated and discussed as also the results of the electrical conductivity and Hall effect measurements. In addition, the anisotropy of the electrical conductivity (σ _⊥/σ _‖) for the obtained crystals was also studied in this work. Finally the photosensitivity was calculated for different levels of illumination as a result of the photoconductivity measurements, which showed that the recombination process in Tl₂S single crystals is a monomolecular process.      

Kinetic phenomena in zero-gap semiconductors CuFeS<Subscript>2</Subscript> and CuFeTe<Subscript>2</Subscript>: Effect of pressure and heat treatment

Electrical resistivity ρ and Hal coefficient R are measured as a function of the temperature (T = 1.7−310 K) and the magnetic field (up to H = 28 kOe) in zero-gap semiconductor CuFeS₂ samples subjected to hydrostatic compression and under various heat-treatment conditions. At low temperatures, anomalies are observed in the kinetic effects related to the presence of ferromagnetic clusters: the magnetoresistance at T = 4.2 K and T = 20.4 K acquires a hysteretic character and thermopower α changes its sign at T < 15 K. The temperature dependence of conduction-electron concentration n in CuFeS₂ has a power form in the temperature range T = 14−300 K, which is characteristic of the intrinsic conductivity in zero-gap semiconductors. In CuFeS₂, we have n(T) ∝ T ^1.2; in isoelectron compound Cu_1.13Fe_1.22Te₂, we have n(T) ∝ T ^1.93. Heat treatment is found to affect the intrinsic conductivity of CuFeS₂, as the action of hydrostatic compression (carrier concentration changes); that is, the carrier concentration changes. However, a power form of the n(T) and ρ(T) dependences is retained.     

Conductivity anisotropy of a TlGaTe<Subscript>2</Subscript> chain single crystal under hydrostatic pressure

Pressure and temperature dependences of the conductivity anisotropy of TlGaTe₂ chain single crystals have been investigated. It has been found that the conductivity anisotropy of TlGaTe₂ can be controlled by choosing the values of temperature and pressure. The temperatures (216, 193, and 77 K) and corresponding pressures (0, 0.31, and 0.71 GPa) have been determined, at which the conductivity of the TlGaTe₂ single crystal becomes isotropic.     

Giant dielectric relaxation in TlGaTe<Subscript>2</Subscript> crystals

The conductivity and temperature-frequency dependences of the permittivity of TlGaTe₂ crystals have been studied. Strong dielectric relaxation has been revealed. It has been shown that the mechanism of dielectric relaxation is associated with hopping of Tl ions over vacancies in the thallium sublattice due to the transition of the system to the superionic state.     

Dielectric characteristics and phase transitions in Tl(InS2) 1 − x (FeSe2) x solid solutions

This paper reports on a study of the electrical conductivity and permittivity of Tl(InS_{2) 1−x} (FeSe_{2) x} crystals as functions of composition and temperature. It has been found that the permittivity decreases in magnitude, while the electrical conductivity increases with increasing x. Crystals Tl(InS_{2) 1−x} (FeSe_{2) x} have been observed to undergo a sequence of phase transitions characteristic of TlInS₂, which manifests itself in formation of anomalies in the σ = f(T) and ɛ = f(T) temperature dependences. It has been shown that as x increases, the phase transition temperatures decrease, while the temperature region within which the incommensurate phase persists broadens slightly.     

Infrared absorption spectra of pure and doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystals

Several weak absorption bands have been observed in the optical absorption spectra of pure and rare-earth-doped YAl₃(BO₃)₄ single crystals in the 3350– 3650 cm⁻¹ wave number region. Two of them, peaking at about 3377 cm⁻¹ and 3580 cm⁻¹ in the 8 K spectra, appear in most of the samples. They are tentatively attributed to the stretching mode of OH⁻ ions incorporated in the crystal during the growth. An additional absorption band at about 5250 cm⁻¹ at 8 K has also been detected in almost all samples. The temperature and polarization dependences of these bands, and their possible origin, are discussed.     

Influence of the misfit of the crystal chemical parameters of Na and Li cations on the dielectric properties of NaNbO<Subscript>3</Subscript>-LiNbO<Subscript>3</Subscript> solid solutions

It is established that the Curie-Weiss temperature of Na_{1 − x} Li _x NbO₃ solid solutions determined by extrapolation of linear portions of the temperature dependence of the reciprocal of the permittivity ɛ⁻¹ from the cubic phase sharply increases with x, although the temperature of the ɛ(T) maximum decreases. It is shown in terms of a simple theoretical model that the experimentally observed change in the dielectric properties of Na_{1 − x} Li _x NbO₃ is well explained under the assumption of formation of a dipole system due to the displacement of Li cations from the center of the cubooctahedral cavity because of the significant steric misfit between the Na and Li cations.     

Electrical instability of LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> crystals

The temperature behavior of I-U curves and the field and temperature dependences of the electrical resistivity and dielectric permittivity of crystals of the LiCu₂O₂ phase have been studied. It was established that the crystals belong to p-type semiconductors and that their static resistivity in the range 80–260 K follows the Mott law ρ=Aexp(T₀/T)^1/4 describing variable-range hopping over localized states. At comparatively low electric fields, the crystals exhibit threshold switching and characteristic S-shaped I-U curves containing a region of negative differential resistivity. In the critical voltage region, jumps in the conductivity and dielectric permittivity are observed. Possible mechanisms of the disorder and electrical instability in these crystals are discussed.     

Optical study of the electronic structure and magnetic ordering in a weak ferromagnet FeBO<Subscript>3</Subscript>

Spectral dependences of the relative permittivity ɛ = ɛ₁ − iɛ₂ of a uniaxial weak ferromagnet FeBO₃ are measured for two principal polarizations in the energy range 0.6–5.6 eV. The positions have been determined for the charge-transfer transitions that make the main contribution to absorption above the bandgap and determine the refractive-index dispersion below the bandgap. The isotropic magnetic contribution to the refractive index has been detected by studying the temperature dependence of the refractive index in the range 100–700 K; its value (≈2 × 10⁻²) is found to be record high for magnetic dielectrics. The energy shift of the effective oscillator, which characterizes the shift of the positions of the charge-transfer transitions due to magnetic ordering, is determined from these data within the framework of a single-oscillator model. The value of the exchange striction in FeBO₃ is determined from optical measurements.     

Soft X-ray resonant scattering study of single-crystal LaSr<Subscript>2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Soft X-ray resonant scattering studies at the Mn L_{II, III}- and the La M_{IV, V}- edges of single-crystal LaSr₂Mn₂O₇ are reported. At low temperatures, below T_N ≈ 160 K, energy scans with a fixed momentum transfer at the A-type antiferromagnetic (0 0 1) reflection around the Mn L_{II, III}-edges with incident linear σ and π polarizations show strong resonant enhancements. The splitting of the energy spectra around the Mn L_{II, III}-edges may indicate the presence of a mixed valence state, e.g., Mn³⁺/Mn⁴⁺. The relative intensities of the resonance and the clear shoulder-feature as well as the strong incident σ and π polarization dependences strongly indicate its complex electronic origin. Unexpected enhancement of the charge Bragg (0 0 2) reflection at the La M_{IV, V}-edges with σ polarization has been observed up to 300 K, with an anomaly appearing around the orbital-ordering transition temperature, T_OO ≈ 220 K, suggesting a strong coupling (competition) between them.     

Quantum oscillations of the resistivity and hall coefficient and the quantum limit in Bi<Subscript>0.93</Subscript>Sb<Subscript>0.07</Subscript> alloys in a magnetic field along the trigonal axis

The dependences of the electrical resistivity ρ and the Hall coefficient R on the magnetic field have been measured for single-crystal samples of the n-Bi_0.93Sb_0.07 semiconductor alloys with electron concentrations in the range 1 × 10¹⁶ cm⁻³ < n < 2 × 10¹⁸ cm⁻³. It has been found that the measured dependences exhibit Shubnikov-de Haas quantum oscillations. The magnetic fields corresponding to the maxima of the quantum oscillations of the electrical resistivity are in good agreement with the calculated values of the magnetic fields in which the Landau quantum level with the number N intersects the Fermi level. The quantum oscillations of the Hall coefficient with small numbers are characterized by a significant spin splitting. In a magnetic field directed along the trigonal axis, the quantum oscillations of the resistivity ρ and the Hall coefficient R are associated with electrons of the three-valley semiconductor and are in phase with the magnetic field. In the case of a magnetic field directed parallel to the binary axis, the quantum oscillations associated both with electrons of the secondary ellipsoids in weaker magnetic fields and with electrons of the main ellipsoid in strong magnetic fields (after the overflow of electrons from the secondary ellipsoids to the main ellipsoid) are also in phase. In magnetic fields of the quantum limit ħω _c /2 ≥ E _F, the electrical conductivity increases with an increase in the magnetic field: σ₂₂(H) ∼ H ^k . A theoretical evaluation of the exponent in this expression for a nonparabolic semiconductor leads to values of k close to the experimental values in the range 4 ≤ k ≤ 4.6, which were obtained for samples of the semiconductor alloys with different electron concentrations. A further increase in the magnetic field results in a decrease of the exponent k and in the transition to the inequality σ₂₂(H) ≤ σ₂₁(H).     

Polarization modes in the Ba<Subscript>2</Subscript>Mg<Subscript>2</Subscript>Fe1<Subscript>2</Subscript>O<Subscript>22</Subscript> multiferroic

The spectra of complex permittivity of a Ba₂Mg₂Fe₁₂O₂₂ single crystal belonging to the family of Y-type hexaferrites have been measured over a wide temperature range (10–300 K) with the aim of determining the dynamic parameters of the phonon and magnetic subsystems in the terahertz and infrared frequency ranges (3–4500 cm⁻¹). A factor-group analysis of the vibrational modes has been performed, and the results obtained have been compared with the experimentally observed resonances. The oscillator parameters of all nineteen phonon modes of E _u symmetry, which are allowed by the symmetry of the Ba₂Mg₂Fe₁₂O₂₂ crystal lattice, have been calculated. It has been found that, at temperatures below 195 and 50 K, the spectral response exhibits new absorption lines due to magnetic excitations.     

Luminescence of CaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript>:Eu crystals

We have studied photoluminescence and thermoluminescence (PL and TL) in CaGa₂Se₄:Eu crystals in the temperature range 77–400 K. We have established that broadband photoluminescence with maximum at 571 nm is due to intracenter transitions 4f⁶ 5d–4f⁷ (⁸S_7/2) of the Eu²⁺ ions. From the temperature dependence of the intensity (log I–10³/T), we determined the activation energy (E _a = 0.04 eV) for thermal quenching of photoluminescence. From the thermoluminescence spectra, we determined the trap depths: 0.31, 0.44, 0.53, 0.59 eV. The lifetime of the excited state 4f6 5d of the Eu²⁺ ions in the CaGa₂Se₄ crystal found from the luminescence decay kinetics is 3.8 μsec. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 112–116, January–February, 2009.