Thermoelectric properties of Sn1−x−yTiySbxO2 ceramics

Thermoelectric properties of Sn_1−x−yTi_y Sb_xO₂ ceramics were investigated in detail. The addition of Sb into SnO₂ matrix increased the electric conductivity, σ. The increase in the σ value should be caused by the increase in the carrier concentration. The Seebeck coefficients of all the samples were negative, which means that these samples have n-type conduction. The samples of this study have porous structure. The maximum Z value of all the samples measured in this study was 2.4 × 10⁻⁵ K⁻¹.     

Synthesis and crystal structure of Ba3Si4C2

SiC powder prepared by the Na flux method at 1023 K for 24 h and Ba were used as starting materials for synthesis of tribarium tetrasilicide acetylenide, Ba₃Si₄C₂. Single crystals of the compound were obtained by heating the starting materials with Na at 1123 K for 1 h and by cooling to 573 K at a cooling rate of −5.5 K/h. The single crystal X-ray diffraction peaks were indexed with tetragonal cell dimensions of a = 8.7693(4) and c = 12.3885(6) Å, space group I4/mcm (No.140). Ba₃Si₄C₂ has the Ba₃Ge₄C₂ type structure which can be described as a cluster-replacement derivative of perovskite (CaTiO₃), and contains isolated anion groups of slightly compressed [Si₄]⁴⁻ tetrahedra and [C₂]²⁻ dumbbells. The electrical conductivity measured for a not well-sintered polycrystalline sample was 2.6 × 10⁻²–7 × 10⁻³ S cm⁻¹ in the temperature range of 370–600 K and slightly increased with increasing temperature. The Seebeck coefficient showed negative values of around −200 to −300 μV K⁻¹.     

Thermoelectric performance of Mg2−xCaxSi compounds

Thermoelectric materials Mg_2−xCa_xSi (x = 0, 0.01, 0.03, 0.05, 0.07, 0.1) compounds have been prepared by vacuum melting followed by hot-pressing. Effects of the substitution of Ca for Mg on phase structures and the thermoelectric properties of the hot-pressed compounds were investigated. It was found that the alloying of Ca in Mg₂Si based compounds increases the electrical conductivity and decreases the Seebeck coefficient of the compounds, due to the electronegativity difference between Ca and Mg. The dimensionless figures of merit of Mg₂Si and Mg_1.99Ca_0.01Si reach, respectively, 0.41 and 0.34 at 660 K.     

Conductivity of a new pyrophosphate Sn0.9Sc0.1(P2O7)1−δ prepared by an aqueous solution method

New pyrophosphate Sn_0.9Sc_0.1(P₂O₇)_1−δ was prepared by an aqueous solution method. The structure and conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ have been investigated. XRD analysis indicates that Sn_0.9Sc_0.1(P₂O₇)_1−δ exhibits a 3 × 3 × 3 super structure. It was found that Sn_0.9Sc_0.1(P₂O₇)_1−δ prepared by an aqueous method is not conductive. The total conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ in open air is 2.35 × 10⁻⁶ and 2.82 × 10⁻⁹ S/cm at 900 and 400 °C respectively. In wet air, the total conductivity is about two orders of magnitude higher (8.1 × 10⁻⁷ S/cm at 400 °C) than in open air indicating some proton conduction. SnP₂O₇ and Sn_0.92In_0.08(P₂O₇)_1−δ prepared by an acidic method were reported fairly conductive but prepared by similar solution methods are not conductive. Therefore, the conductivity of SnP₂O₇-based materials might be related to the synthetic history. The possible conduction mechanism of SnP₂O₇-based materials has been discussed in detail.     

Structures, electrical and thermal expansion properties of Sr-doped La2Mo2O9 oxide-ion conductors

The oxide-ion conductors (La_1−xSr_x)₂Mo₂O_9−δ (x = 0.01–0.08) were prepared by means of a conventional solid-state reaction. The effects of Sr doping for La site on the structures, electrical and thermal expansion properties of the oxide-ion conductor La₂Mo₂O₉ were investigated using X-ray diffraction, direct current four-probe method, thermal dilatometer and scanning electron microscopy, respectively. The results show that the lattice constants were first decreased, then increased, and decreased again with the increase of Sr doping content. The solid solubility of Sr in (La_1−xSr_x)₂Mo₂O_9−δ is x = 0.07. The sinterability of samples is markedly improved with the increase of Sr doping content. The sintered density of sample x > 0.07 is higher than 96% of its theoretical density. When x > 0.02, doping Sr in La₂Mo₂O₉ can inhibit the excessive growth of grains, thus increases the sintered density of samples. The structural transition temperature shifts to the low side with the increase of Sr doping content, and the phase transition is completely suppressed when the doping content reaches 0.07. The conductivity of sample increases with the increase of Sr doping content. The conductivity of sample x = 0.07 reaches a maximum of 0.078 S/cm and 0.101 S/cm at 800 °C and 850 °C, respectively. In this study, it was demonstrated that doping 7 mol% Sr for La site not only can completely suppress the structural phase transition in La₂Mo₂O₉, but also can effectively enhance electrical conductivity of samples at higher temperature.     

Electrical behaviour of hydridofluorides of potassium–calcium KCaH3−xFx with x = 1, 1.5, 2, 2.5

This paper reports the results of the electrical conductivity measurements for KCaH_3−xF_x series with (x = 1, 1.5, 2, 2.5) in the temperature range 298–503 K.The activation energy of the electrical conductivity for the studied compounds depends on hydrogen amount and Reau's criteria. Differential thermal analysis curves were measured in the same temperature range 298–503 K.Possible correspondence between preferential order given by X-ray diffraction, thermal behaviour and electrical properties are discussed.     

Unexpected influence of substrate temperature on the properties of P-doped ZnO

The electrical conductivity of phosphorus-doped ZnO (P:ZnO) was found to change with sputter substrate temperature. Unexpectedly, n-type conductivity was obtained for samples deposited at substrate temperatures of 200, 250 and 300 °C, but p-type conductivity was achieved for samples deposited at room temperature (RT). The type of a ZnO sample was determined and cross-checked by using three different techniques: the Hall effect, the Seebeck effect and magnetic field-dependent Hall voltage measurements. The n-type samples had conductivities of 11–45 S cm⁻¹ and the p-type sample possessed a conductivity of 0.74 S cm⁻¹. Furthermore, significantly different activation energies were found for the n-type (10 meV) and p-type (134 meV) P:ZnO samples, which were in good agreement with the positions of the donor and acceptor levels in the band structure reported in the literature. SIMS profiling measurement revealed that the oxygen concentration in the P:ZnO film deposited at RT was clearly higher than those in the films deposited at higher substrate temperatures. The results and relevant mechanisms were discussed. It appears that the n-type or p-type conductivity of a P:ZnO sample was determined mainly by the dominance of the n-type defect donors or the P induced acceptors.     

Pilot plant scale preparation of dodecylbenzene sulfonic acid doped polyaniline in ethanol/water solution: Control of doping, reduction of purification time and of residues

Aiming to produce polyaniline doped with dodecylbenzene sulfonic acid on a pilot plant scale using a 10 L reactor, the synthesis was optimized on a bench scale using a 2³ factorial design, involving the variables: K parameter, DBSA/aniline molar ratio (Q) and final aniline concentration (C). The nominal yield and electrical conductivity were used as control parameters. An ethanol/water (2:5, v/v) solution replaced water as solvent. The samples were characterized by electrical conductivity measurements, infrared spectroscopy, X-ray diffraction, elemental analysis, thermogravimetry and density. The influence of the washing solvent volumes and storage time of oxidizer on the nominal yield and electrical conductivity of PAni/DBSA were also investigated. By using ethanol/water as solvent it was possible to reduce the filtration time, to eliminate the purification step and to control the content of DBSA in the polyaniline bulk, maintaining the principal characteristics, like electrical conductivity and density. The doped polymer was obtained with electrical conductivity in the range of 10⁻¹ to 10⁻³ S cm⁻¹, depending on the dopant concentration. Freshly purchased ammonium peroxydisulfate must be used for higher yields and better reproducibility.     

Fabrication and study on Ni1−xFexO-YSZ anodes for intermediate temperature anode-supported solid oxide fuel cells

Bimetal oxides Ni_1−xFe_xO (x = 0.01, 0.04, 0.08, 0.1, 0.15, 0.2, 0.4, 0.5) were synthesized and studied as anodes for intermediate temperature solid oxide fuel cells (SOFCs) based on yttria-stabilized zirconia (YSZ) film electrolyte. A single cell consisted of Ni_1−xFe_xO-YSZ anode, YSZ electrolyte film, LSM–YSZ composite cathode was prepared and tested at the temperature from 600 °C to 850 °C with humidified hydrogen (75 ml min⁻¹) as fuel and ambient air as oxidant. It was found that the cell with Ni_0.9Fe_0.1O-YSZ anode showed the highest power density, 1.238 W cm⁻² at 850 °C, among the cells with different anode composition. The promising performance of Ni_1−xFe_xO as anode suggests that bimetal anodes are worth studied for SOFCs in future.     

Crystal, electric transport properties and electronic structures of the Ti5Me1−xSb2+x series of compounds (MeCr, Mn, Fe, Co, Ni, Cu)

The Ti₅Me_1−xSb_2+x compounds where MeCr, Mn, Fe, Co, Ni, Cu, were synthesized and their crystal structure was determined (W₅Si₃ structure type, space group I4/mcm). The transport properties were investigated by means of electrical resistivity and Seebeck coefficient measurements in the temperature range 80–380 K. All the investigated compounds exhibit metallic-like type of conductivity confirmed by electronic structure calculations based on Density Functional Theory.     

Thermoelectric properties of hot-pressed Zn4Sb3−xTex

A series of samples have been fabricated through vacuum melting method followed by hot-pressing for Zn₄Sb_3−xTe_x (x = 0.02–0.08), XRD patterns indicated that all the samples were single-phased β-Zn₄Sb₃. Electrical conductivity and Seebeck coefficient were evaluated in the temperature range of 300–700 K, showing p-type conduction. The thermoelectric figure of merit (ZT) was increased with the increase of Te content. ZT values of 0.8 and 1.0 were obtained at 673 K for Zn_4.08Sb₃ and Zn₄Sb_2.92Te_0.08, respectively.     

Room-temperature interface state analysis of Au/Poly(4-vinyl phenol)/p-Si structure

The Poly(4-vinyl phenol) insulator layer was grown by spin coating technique onto p-Si substrate. Diode ideality factor (n), insulator layer thickness (δ), space charge region width (W_D), interface state density (N_ss), series resistance (R_s), acceptor concentration (N_A) of the Au/Poly(4-vinyl phenol)/p-Si structure have been extracted from the current–voltage (I–V), frequency dependent capacitance–voltage (C–V) and conductance–voltage (G–V) measurements. It is pointed out that the interface states lead to deviation of the ideality factor value from 1 and frequency dispersion of the C–V characteristics. N_ss profiles as a function of (E_ss−E_v) obtained using I–V and low frequency C–V measurements are in good agreement. N_ss values varying between 10¹² and 10¹³ eV⁻¹ cm⁻² mean that Poly(4-vinyl phenol) is a candidate for insulator layer forming on Si as powerful as SiN₄, SnO₂, TiO₂.     

Structural, magnetic and electrical transport properties for a series of La1−xSrxFe1−xMnxO3 (0.3 ≤ x ≤ 0.7) compounds

The structural, electrical transport and magnetic properties have been studied for compounds: La_1−xSr_xFe_1−xMn_xO₃ (0.3 ≤ x ≤ 0.7). The lattice parameter, a, first decreases with x, and followed by an increase when Sr²⁺ and Mn⁴⁺ was continuously doped. The cell parameters, b and c, slightly decrease with coupled substitution of Sr²⁺ for La³⁺ and Mn⁴⁺ for Fe³⁺. In the paramagnetic temperature range, formation of magnetic clusters is suggested; the sizes of clusters decrease with x up to 0.5, following that they increase sharply with continuing doping. The electrical behaviors of all specimens demonstrate insulators and the electrical resistivity increases with content of Mn⁴⁺ and Sr²⁺ ions doped. A variable range hopping model is suitable to describe electrical transport process for the compounds at low temperature. At high temperature the electrical transport process can be described by bipolaron model for all compounds.     

Investigation of DC conductivity and switching phenomenon of Se80Te20−xGex amorphous system

Se₈₀Te_20−xGe_x (x = 5, 7 and 10 at%) chalcogenide glass system was prepared by the conventional melt-quenching technique. Thin films of different thicknesses (283–823 nm) were prepared by thermal evaporation technique. The DC conductivity and switching properties were investigated in the temperature range 303–373 K below the corresponding glass transition temperature. The obtained results of DC conductivity showed that it decreases with decreasing Te content in the considered system, while it increases with temperature as well as with film thickness through the studied range. The conduction activation energy has two values E_σ1 and E_σ2 indicating the presence of two different conduction mechanisms through the studied range of temperature. The obtained results of the temperature dependence of DC conductivity are explained in accordance with Mott and Davis model. The switching effect in amorphous films was also investigated. The switching phenomenon for these compositions was of the memory type. The mean value of the threshold voltage increases linearly with increasing film thickness in the range 283–823 mm, while it decreases exponentially with increasing temperature in the investigated range. Values of the threshold voltage and power activation energies were obtained for the investigated compositions. The obtained results agree with the electrothermal model for the switching process.     

Synthesis and properties of polyaniline–cobalt coordination polymer

Polyaniline–cobalt coordination polymer (abbreviated as PANI-Co) was synthesized using peroxydisulphate as an oxidant in the solution containing 0.1 mol dm⁻³ aniline, 0.5 mol dm⁻³ HCl and an adequate content of CoCl₂·6H₂O at room temperature. The conductivity of PANI-Co was 0.5 S cm⁻¹. The cyclic voltammogram results indicated that the PANI-Co film was of electrochemical activity, and the EPR spectrum showed that there were unpaired electrons in the PANI-Co. The relationship between magnetization (M) and the applied magnetic field (H) suggests that PANI-Co was soft ferromagnetic material at room temperature. Thus, the PANI-Co was both conductive and ferromagnetic. Moreover, UV–vis and FTIR spectra showed that there existed a strong interaction between Co²⁺ and PANI chains.     

Filtered vacuum arc deposition of undoped and doped ZnO thin films: Electrical, optical, and structural properties

Filtered vacuum (cathodic) arc deposition (FVAD, FCVD) of metallic and ceramic thin films at low substrate temperature (50-400 °C) is realized by magnetically directing vacuum arc produced, highly ionized, and energetic plasma beam onto substrates, obtaining high quality coatings at high deposition rates. The plasma beam is magnetically filtered to remove macroparticles that are also produced by the arc. The deposited films are usually characterized by their good optical quality and high adhesion to the substrate. Transparent and electrically conducting (TCO) thin films of ZnO, SnO₂, In₂O₃:Sn (ITO), ZnO:Al (AZO), ZnO:Ga, ZnO:Sb, ZnO:Mg and several types of zinc-stannate oxides (ZnSnO₃, Zn₂SnO₄), which could be used in solar cells, optoelectronic devices, and as gas sensors, have been successfully deposited by FVAD using pure or alloyed zinc cathodes. The oxides are obtained by operating the system with oxygen background at low pressure. Post-deposition treatment has also been applied to improve the properties of TCO films.The deposition rate of FVAD ZnO and ZnO:M thin films, where M is a doping or alloying metal, is in the range of 0.2-15 nm/s. The films are generally nonstoichiometric, polycrystalline n-type semiconductors. In most cases, ZnO films have a wurtzite structure. FVAD of p-type ZnO has also been achieved by Sb doping. The electrical conductivity of as-deposited n-type thin ZnO film is in the range 0.2-6 × 10^− 5 Ω m, carrier electron density is 10²³-2 × 10²⁶ m^− 3, and electron mobility is in the range 10-40 cm²/V s, depending on the deposition parameters: arc current, oxygen pressure, substrate bias, and substrate temperature. As the energy band gap of FVAD ZnO films is ∼ 3.3 eV and its extinction coefficient (k) in the visible and near-IR range is smaller than 0.02, the optical transmission of 500 nm thick ZnO film is ∼ 0.90.     

Preparation of polyaniline–titanium dioxide hybrid materials in supercritical CO2

Polyaniline–titanium dioxide (PANI–TiO₂) hybrid materials were synthesized in supercritical CO₂ using two different methods. In the first method, separately synthesized TiO₂ particles were mixed with aniline to perform polymerization in supercritical CO₂. The second method included the preparation of aniline–TiO₂ hybrids through a sol–gel reaction of titanium isopropoxide in the presence of aniline. Further polymerization of aniline–TiO₂ hybrids in supercritical CO₂ produced PANI–TiO₂ hybrid particles. The final products showed the intrusion of PANI into the internal structure of TiO₂. The PANI–TiO₂ hybrid materials were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), electrical conductivity (EC), Fourier-transform infrared (FT-IR) and X-ray diffraction (XRD) measurements. PANI–TiO₂ nano-composites synthesized with the first method showed a relatively low electrical conductivity of 3.78 × 10⁻² S/cm at 20 °C. TGA suggested that the particles contained 40.6% TiO₂ by mass and showed a strong interaction at the interface of TiO₂ and PANI. The electrical conductivity of the hybrid particles produced using the second method increased to 7.75 × 10⁻² S/cm and the TGA results showed 34.4% TiO₂ by mass. Through SEM and TEM analyses it was confirmed that the PANI has been interpenetrated into the three-dimensional network of the TiO₂ when the second method was used.     

Electronic transport properties of liquid Ga–Zn alloys

In the present work, the electrical resistivity and the absolute thermoelectric power (Seebeck coefficient) of the liquid Ga_x–Zn_1−x alloys have been measured at different concentrations as functions of temperature. The liquid alloy is contained in a quartz cell fitted with tungsten and tungsten-rhenium electrodes. The thermal conductivity is deduced using Wiedemann–Franz law. To interpret our experimental data, we used a quantum mechanical calculation of the electrical resistivity ρ and of the thermoelectric power S of Ga_x–Zn_1−x alloys known as the “Faber–Ziman” formalism.     

Electrical and electrochemical properties of γ-Li2CuZrO4

The γ-Li₂CuZrO₄ with a double rock-salt structure, as a lithium-ion compound, has never been reported on their physical and physicochemical properties. The γ-Li₂CuZrO₄ was prepared by a solid-state reaction process. X-ray diffraction was used to analyze the structure of the products. Its electrical properties were characterized by both DC and AC measurements in the temperature range from 133 to 1273 K. Cyclic voltammetry and galvanostatic cell cycling were also employed to evaluate its electrochemical performance. It is found to be a pure electronic semiconductor with a fairly high conductivity (10⁻⁵ S/cm at 133 K, 10⁻² S/cm at 300 K and 10⁻¹ S/cm at 1173 K). The average activation temperature is 14.4 kJ/mol. When increasing the temperature above 1073 K, a phase transition from γ to β takes place. When reacting with lithium in an electrochemical cell, γ-Li₂CuZrO₄ decomposes into three phases during the initial discharge process, and possesses a reversible capacity of about 70 mAh/g.     

Raman and infrared study of 100 MeV swift Ag heavy ion irradiation effects in CaSO4·2H2O single crystals

The modifications of calcium sulphate (CaSO₄·2H₂O) single crystals are investigated by means of Raman and Fourier transform infrared spectroscopy (FT-IR) using 100 MeV Ag⁸⁺ ions in the fluence range 1 × 10¹¹ to 5 × 10¹³ ions/cm². It is observed that the intensities of the Raman modes decrease with increase in ion fluence. We determined damage cross-section (σ) for all the Raman active modes and found to be different for different Raman modes. Further, FT-IR studies have been carried out to confirm surface amorphisation for a fluence of 1 × 10¹³ ions/cm². It is observed that the absorption peaks at 1132–1156 cm⁻¹ corresponds to ν₃(SO₄²⁻) mode. The decrease in Raman peaks intensity with ion fluence is attributed to degradation of ν₃(SO₄²⁻) modes present on the surface of the sample.