Structure and electrical properties of SrO-borovanadate (V2O5)0.5(SrO)0.5−y(B2O3)y glassses

SrO-borovanadate glasses with nominal composition (V₂O₅)_0.5(SrO)_0.5−y(B₂O₃)_y, 0.0≤y≤0.4 were prepared by a normal quench technique and investigated by direct current (DC) electrical conductivity, inductively coupled plasma (ICP) spectroscopy, infrared (IR) spectroscopy and X-ray powder diffraction (XRD) studies in an attempt to understand the nature of mechanism governing the DC electrical conductivity and the effect of addition of B₂O₃ on the structure and electrical properties of these glasses. XRD patterns confirm the amorphous nature of the present glasses and actual compositions of the glasses were determined by ICP spectroscopy. The temperature dependence of DC electrical conductivity of these glasses has been studied in terms of different hopping models. The IR results agree with previous investigations on similar glasses and it has been concluded that similar to SrO-vanadate glasses, metavandate chain-like structures of SrV₂O₆ and individual VO₄ units also occur in SrO-borovanadate glasses. The SrV₂O₆ and VO_n polyhedra predominate in the low B₂O₃-containing SrO-borovanadate glasses as B substitutes into the V sites of the various VO_n polyhedra and only when the concentration of B₂O₃ exceeds the SrO content do BO_n structures appear. This qualitative picture of three distinct structural groupings for Sr-vanadate and Sr-borovanadate glasses is consistent with the proposed glass structure on previous IR and extended X-ray absorption fine structure (EXAFS) studies on these types of glasses. The conductivity results were analyzed with reference to theoretical models existing in the literature and the analysis shows that the conductivity data are consistent with Mott's nearest neighbor hopping model. Analysis of the conductivity data shows that they are consistent with Mott's nearest neighbor hopping model. However, both Mott VRH and Greaves models are suitable to explain the data. Schnakenberg's generalized polaron hopping model is also consistent with temperature dependence of activation energy. However, various model parameters such as density of states, hopping energy, etc. obtained from the best fits were not found to be in accordance with the prediction of the Mott model.     

The thermoelectric power of charge-density-wave conductors Rb0.3MoO3 and Rb0.15K0.15MoO3

The thermoelectric power (TEP) of the quasi-one-dimensional charge-density-wave (CDW) conductors rubidium blue bronze Rb_0.3MoO₃ and its alloy Rb_0.15K_0.15MoO₃ were measured in the temperature range 80-280 K. The result showed a sign change from a small positive value to a great negative value where the Peierls transition temperatures (T_p) are 183 and 180 K for Rb_0.3MoO₃ and Rb_0.15K_0.15MoO₃, respectively. Above T_p, the TEP for both samples can be described with the empirical relation S=AT+B; while below T_p, the TEP fits well the relation S=AT+B/T based on the experimental data. The Fermi energies ε_F for Rb_0.3MoO₃ and Rb_0.15K_0.15MoO₃ are estimated to be 1.55 and 0.53 eV, respectively.     

Structure and electrical conductivity of a novel inorganic solid electrolyte: Na14.5[Al(PO4)2F2]2.5[Ti(PO4)2F2]0.5 (NATP)

A novel inorganic solid electrolyte with a layered framework structure stable up to 1043 K, Na_14.5[Al(PO₄)₂F₂]_2.5[Ti(PO₄)₂F₂]_0.5 (NATP), has been hydrothermally prepared and characterized by single-crystal and powder X-ray diffraction techniques, X-ray fluorescence (XRF) analysis, IR spectroscopic measurement, thermogravimetric and differential thermal analysis (TGA and DTA). NATP crystallizes in the acentric hexagonal space group P3 with a=10.448(2), b=10.448(2), , Z=1, containing a large number of Na⁺ cations in the interlamellar space and the cavities of its framework. There are six different crystallographic Na⁺ cationic sites, in which 8% Na(5) and 12% Na(6) sites are vacant. Electrical conductivity measurements show that Na⁺ cations exhibit a high mobility with two domains for the electrical conductivity versus temperature.     

The effect of Mn substitution on thermoelectric properties of Ca3MnxCo4−xO9 at low temperatures

The effects of partial substitution of Mn for Co on the thermoelectric properties of Ca₃Mn_xCo_4−xO₉ (x=0, 0.03, 0.9), prepared by sol-gel process, were investigated at the temperatures from 380 K down to 5 K. The results indicate that the substitution of Mn for Co results in increase in thermopower at temperatures >∼80 K, and substantial (23-31% at 300 K) decrease in lattice thermal conductivity in the whole temperature range investigated. The temperature behavior of ZT suggests that Ca₃Mn_xCo_4−xO₉ with light Mn substitution would be a promising candidate for high-temperature thermoelectric applications.     

Enhanced thermoelectric properties of bismuth intercalated compounds BixTiS2

The thermoelectric properties of Bi intercalated compounds Bi_xTiS₂ have been investigated at the temperatures from 5 to 310 K. The results indicate that Bi intercalation into TiS₂ leads to substantial decrease of its electrical resistivity (one order low for x=0.05 and two orders low for x=0.15, 0.25 at 300 K) and lattice thermal conductivity (22, 115 and 158% low at 300 K for x=0.05, 0.15 and 0.25, respectively). Specially, the figure of merit, ZT, of lightly intercalated compound Bi_0.05TiS₂ has been improved at all temperatures investigated, and specifically reaches 0.03 at 300 K, which is about twice as large as that of TiS₂.     

Kondo lattice behaviour in CePt2(Si1−xSnx)2 alloys

Measurements of electrical resistivity are presented for polycrystalline alloys in the CePt₂(Si_1−xSn_x)₂ system. Results of X-ray diffraction indicate that the tetragonal region of the CePt₂(Si_1−xSn_x)₂ alloy system that is amenable for study only extends up to x=0.3. The resistivity maximum characteristic of a Kondo lattice is observed at a temperature T_max=63 K for the parent compound CePt₂Si₂ and shifts to lower temperatures with increase in Sn content. The compressible Kondo lattice model is applied to describe the results of T_max in terms of the on-site Kondo exchange interaction J and the electron density of states at the Fermi level N(E_F). A value of |JN(E_F)|=0.060±0.009 for the parent compound is obtained from the experimental results.     

Modified texture and high temperature transport properties of doubly substituted BaxAgyCa2.8Co4O9 thermoelectric oxide

Doubly substituted polycrystalline compound bulk samples of Ba_xAg_yCa_2.8Co₄O₉ were prepared via citrate acid sol-gel method followed by spark plasma sintering. The phase composition, orientation, texture and high temperature electrical properties were systematically investigated. The results showed that the orientation and the texture could be modified by altering ratio of Ba to Ag. The resistivity and the Seebeck coefficient of substituted samples were decreased by decreasing Ba/Ag ratio except for that of Ba_0.1Ag_0.1Ca_2.8Co₄O₉ sample with lowest electrical resistivity (7.2 mΩ cm at 973 K), moderately high Seebeck coefficient (172 μV/K at 973 K) and improved power factor (0.42 mW/mK² at 973 K).     

Optical constants of Cu(In0.7Ga0.3)5Se8 and Cu(In0.4Ga0.6)5Se8 crystals

Variable angle spectroscopic ellipsometry has been applied to characterize the optical constants of bulk Cu(In_0.7Ga_0.3)₅Se₈ and Cu(In_0.4Ga_0.6)₅Se₈ crystals grown by the Bridgman method. The spectra were measured at room temperature over the energy range 0.8-4.4 eV. Adachi’s model was used to calculate the dielectric functions as well as the spectral dependence of complex refractive index, absorption coefficient, and normal-incidence reflectivity. The calculated data are in good agreement with the experimental ones over the entire range of photon energies. The parameters such as strength, threshold energy, and broadening, corresponding to the E₀, E_1A, and E_1B interband transitions, have been determined using the simulated annealing algorithm.     

Influence of negative pressure on thermoelectric properties of Sb2Te3

We investigated the influence of negative pressure on the electrical conductivity, the Seebeck coefficient, and the power factor of Sb₂Te₃. We performed first-principles calculations with the linearized-augmented plane-wave method considering negative hydrostatic pressure in the range from zero to −2 GPa and doping for electrons and holes up to 10²⁰ cm⁻³. Our results predict a significant increase of the Seebeck coefficient and the power factor under negative pressure for certain doping concentrations.     

Anomalous thermoelectric power behaviour in PrSn3 and NdSn3

Results of the thermoelectric power (TEP) measurements done on monocrystalline samples of RESn₃ compounds (RE=La, Pr, Nd, and Gd) are presented for the temperature range of 5.5-300 K. It was found that the TEP is positive and weakly temperature dependent at temperatures T>100 K. For T<100 K pronounced anomalies have been observed for the PrSn₃ and the NdSn₃ compounds in the vicinity of 10 K.We argue that the Kondo and crystal field effects cause these anomalies. A shape of the TEP anomaly found for PrSn₃ resembles very much that observed in the electrical resistivity.     

Analysis of the Ge1−xCx films deposited by MFMST

Ge_1−xC_x films deposited by using a medium frequency magnetron sputtering technique (MFMST) were analyzed with X-ray photoelectron and Raman spectroscopy. The deposited Ge_1−xC_x films consist of C, Ge, GeC and GeO_y. The GeC content in the Ge_1−xC_x films linearly decreases, and the C content linearly increases with increasing deposition temperature from 150 to 350 °C. The GeC content decreases from 11.6% at a substrate bias of 250 V to a lowest value of 9.6% at 350 V, then increases again to 10.4% at 450 V. While the C content increases from 49.0% at the bias of 250 V to a largest value of 58.0% at 350 V and then maintains this level at 450 V. It is found that selecting a bias parameter seems more effective than deposition temperature if we want to obtain a higher content of GeC in the deposited films. In addition, a new method is presented in this paper to estimate the changes of GeC content in the Ge_1−xC_x films by observing the shifts of Ge-Ge LO phonon peak in Raman spectra for the Ge_1−xC_x films. The related mechanism is also discussed in this paper.     

High-temperature thermoelectric properties of Ca3Co4O9+δ with Eu substitution

We have prepared polycrystalline Ca_3−xEu_xCo₄O_9+δ (x=0, 0.15, 0.3 and 0.45) samples using a sol-gel process followed by SPS sintering and investigated the Eu substitution effects on their high-temperature thermoelectric properties. With the Eu substitution, both the electrical resistivity and thermopower increase monotonously. This could be attributed to the decrease of hole concentrations by substitution of trivalent Eu³⁺ for divalent Ca²⁺. The Eu substituted samples (x=0.15, x=0.3) have lower thermal conductivity than Ca₃Co₄O_9+δ due to their lower electronic and lattice thermal conductivity. The dimensionless figure of merit ZT reaches 0.3 at 1000 K for the sample of Ca_2.7Eu_0.3Co₄O_9+δ.     

The magnetic susceptibility of hydrogen-doped partially crystalline (Zr76Ni24)1−xHx metallic glasses

The magnetizations of Zr₇₆Ni₂₄ metallic glass and hydrogen-doped partially crystalline (Zr₇₆Ni₂₄)_1−xH_x metallic glasses have been measured in the temperature range 10-300 K and magnetic fields up to 2 T for various dopant concentrations (x=0, 0.024, 0.043, 0.054). It is found that the samples are paramagnetic and magnetic susceptibility at room temperature, χ(300 K), shows a nonmonotonic behaviour upon hydrogenation. The values of χ(300 K) of the hydrogen-doped partially crystalline (Zr₇₆Ni₂₄)_1−xH_x metallic glasses are reduced with increase in hydrogen content up to x=0.043, whereas for x=0.054, an enhancement of χ(300 K) has been revealed. The magnetic susceptibility is weakly temperature dependent down to 110 K, below which an increase is observed. A shallow minimum exists between 90 and 120 K. The form and magnitude of the observed temperature dependence of the magnetic susceptibility are well accounted for by the sum of the quantum corrections to the magnetic susceptibility. Hydrogen reduces the electronic diffusion constant and influences strongly the quantum interference at defects, slowing down the spin diffusion and enhancing the magnetic susceptibility in the temperature range from 110 down to 10 K.     

Dielectric parameters in Se70Te30 and Se70Te28Zn2 chalcogenide glasses

Temperature and frequency dependence of dielectric constant (ε′) and dielectric loss (ε″) are studied in glassy Se₇₀Te₃₀ and Se₇₀Te₂₈Zn₂. The measurements have been made in the frequency range (8-500 kHz) and in the temperature range 300 to 350 K. An analysis of the dielectric loss data shows that the Guintini's theory of dielectric dispersion based on two-electron hopping over a potential barrier is applicable in the present case.No dielectric loss peak is observed in glassy Se₇₀Te₃₀. However, such loss peaks exist in the glassy Se₇₀Te₂₈Zn₂ in the above frequency and temperature range. The Cole-Cole diagrams have been used to determine some parameters such as the distribution parameter (α), the macroscopic relaxation time (τ₀), the molecular relaxation time (τ) and the Gibb's free energy for relaxation (ΔF).     

DC and AC conductivities of (As2S3)100−x(AsSe0.5Te0.5I)x chalcogenide glasses

The DC and AC conductivities of samples from the system (As₂S₃)_100−x(AsSe_0.5Te_0.5I)_x, where x=0, 5, 10, 15, 20, 25, 30, 35, 50, 70 and 90 mol%, were measured as a function of temperature. Besides, the AC conductivities of the samples with x=10 and 30 were measured as a function of frequency from room temperature to the glass transition temperature. The DC conductivity dependence on temperature is of the Arrhenius type, whereas the value of the pre-exponential factor suggests the electrical conduction by localized states in the band tails and by localized states near the Fermi level. The small values of the conduction activation energy (10⁻²-10⁻¹ eV) obtained at higher frequencies suggest that the conduction in these materials is due to hopping of charge carriers between close defect states near the Fermi level.     

Electrical properties of KTiOPO4 single crystal in the temperature range from −100 °C to 100 °C

The electrical property of a KTiOPO₄ single crystal was studied by means of a dielectric spectroscopy method in the temperature range from −100 to 100 °C. Dielectric dispersion began at a temperature, T_S=−80 °C. It is believed that this dielectric dispersion is related to the ionic hopping conduction, which arises mainly from the jumping of K⁺ ions. The activation energy concerned with hopping conduction is E_a∼0.20 eV above T_S. T_S=−80 °C can be the minimum temperature for the hopping K⁺ ion.     

Thermally Activated Photoconduction and Alternating-Current Conduction in Se75Ge20Ag5 Chalcogenide Glass: Investigation of Meyer--Neldel Rule

We report on the observation of Meyer-Neldel rule in glassy Se75Ge20Ag5 alloy where AE is varied by two different methods. In the first approach, the intensity of light varies while measuring the photoconductivity in amorphous thin films of Se75Ge20Ag5 instead of changing composition of the glassy system. In the second approach, the variation of ac conductivity with temperature is found to be exponential and the activation energy is found to vary with frequency.     

Optical and thermoelectric characterizations of electroplated n-Bi2(Te0.9Se0.1)3

Bismuth selenotelluride (Bi₂(Te_0.9Se_0.1)₃) films were electrodeposited at constant current density from acidic aqueous solutions with Arabic gum in order to produce thin films for miniaturized thermoelectric devices. X-ray fluorescence spectroscopy determined film compositions. X-ray diffraction pattern shows that the films as deposited are polycrystalline, isostructural to Bi₂Te₃ and covered by crystallites. Mueller-matrix analysis reveals that the electroplated layers are optically like an isotropic medium. Their pseudo-dielectric functions were determined using mid-infrared spectroscopic ellipsometry. Tauc-Lorentz combined with Drude dispersion relations were successfully used. The energy band gap E_g was found to be about 0.15 eV. Moreover, the fundamental absorption edge was described by an indirect optical band-to-band transition. From Seebeck coefficient measurement, films exhibit n-type charge carrier and the value of thermoelectric power is about −40 μV/K.     

Magnetic and transport properties of YbRhIn5 and YbIrIn5 single crystals

Single crystals of YbRhIn₅ and YbIrIn₅ have been grown by flux method. The crystals were characterized by means of X-ray diffraction, magnetic and electrical transport measurements. Both compounds were found to be weak diamagnets with metallic character of the electrical conductivity and the Seebeck coefficient.     

The effect of pressure on the spin density wave transition in the layered cobaltites [Ca2CoO3]0.62[CoO2] and [Ca2Co4/3Cu2/3O4]0.62[CoO2]

In order to investigate the pressure effect on the magnetism in the layered cobaltites, positive muon spin rotation and relaxation μ⁺SR experiments have been carried out up to 1.3 GPa using c-aligned polycrystalline samples of [Ca₂CoO₃]_0.62[CoO₂] and [Ca₂Co_4/3Cu_2/3O₄]_0.62[CoO₂]. A transverse field μ⁺SR experiment indicates that the transition temperature to an incommensurate spin density wave IC-SDW state is independent of hydrostatic pressure up to 1.3 GPa for the both compounds. Furthermore, there are no changes in the spontanious muon precession frequency in zero field at 5 K even under 1.3 GPa. These results strongly suggest that the IC-SDW exists not in the rocksalt-type block ([Ca₂CoO₃] and/or [Ca₂Co_4/3Cu_2/3O₄]) but in the CoO₂ plane.