Thermoelectric properties of the tetradymite-type Bi2Te2S-Sb2Te2S solid solution

The thermoelectric properties of the tetradymite-type Bi_2−xSb_xTe₂S solid solution (0 ≤ x ≤ 2) are reported for the temperature range 5-300 K. The properties of non-stoichiometric, Cl and Sn doped n- and p-type variants are reported as well. The Seebeck coefficients for these materials range from −170 to +270 μV K⁻¹ while the resistivities range from those of semimetals, 2 mΩ cm, to semiconductors, >1000 mΩ cm. Thermal conductivities were low for most compositions, typically 1.5 W m⁻¹ K⁻¹. Nominally undoped Bi₂Te₂S shows the highest thermoelectric efficiency amongst the tested materials with a ZT = 0.26 at 300 K that decreased to 0.04 at 100 K. The crystal structure of Sb₂Te₂S, a novel tetradymite-type material, is also reported.     

Supercritical hydrothermal synthesis of Cu2O(SeO3): Structural characterization, thermal, spectroscopic and magnetic studies

Cu₂O(SeO₃) has been synthesized in supercritical hydrothermal conditions, using an externally heated steel reactor with coupled hydraulic pump for the application of high pressure. The compound crystallizes in the P2₁3 cubic space group. The unit cell parameter is a = 9.930(1) Å with Z = 12. The crystal structure has been refined by the Rietveld method. The limit of thermal stability is, approximately, 490 °C. Above this temperature the compound decomposes to SeO₂(g) and CuO(s). The IR spectrum shows the characteristic bands of the (SeO₃)²⁻ oxoanion. In the diffuse reflectance spectrum two intense absorptions characteristic of the Cu(II) cations in five-coordination are observed. The ESR spectra are isotropic from room temperature to 5 K, with g = 2.11(2). The thermal evolution of the intensity and line width of the signals suggest a ferromagnetic transition in the 50-45 K range. Magnetic measurements, at low temperatures, confirm the existence of a ferromagnetic transition with a critical temperature of 55 K.     

Subsolidus phase equilibria and the Li5Nd4FeO10 phase in the Li2O-Nd2O3-Fe2O3 system

A survey of the subsolidus phase equilibria in the system Li₂O-Nd₂O₃-Fe₂O₃ was made at subsolidus temperatures in the range 1000-1050 °C. A ternary phase was identified. The phase is centered on Li₅Nd₄FeO₁₀, with a cubic lattice a = 11.9494 Å. The compound melts incongruently at 1105 °C. The magnetic susceptibility was measured in the temperature range 4-300 K. The compound is paramagnetic in the temperature range 150-300 K and follows the Curie-Weiss law. At about T_N = 10 K, a long-range magnetic ordering is observed.     

Temperature evolution of structure and magnetic properties in the perovskite Sr2MnSbO6

The structural and magnetic properties of the perovskite Sr₂MnSbO₆ have been studied. Combining neutron and X-ray powder diffraction data, the temperature evolution of the structural parameters was investigated with the Rietveld method between 2 and 1000 K. The crystal structure is tetragonal (space group I4/m) within the temperature interval of 2-750 K and cubic (space group Fm-3m) above 750 K. Both octahedral B-site positions were found to be partially occupied by Mn and Sb, but with different Mn/Sb ratios. The magnetic susceptibilities showed irreversibility between field cooled and zero-field cooled (ZFC) conditions and spin glass like magnetic dynamics including aging and memory phenomena at temperatures below 30 K; all appearing well above a broad maximum at 13 K in the ZFC susceptibility curves. This suggests that the material reaches an unconventional spin-glass state at low temperatures, possibly arising from a competitive situation between the double exchange (ferromagnetism) and the super-exchange (antiferromagnetism). Neutron diffraction patterns showed no evidence of a long-range magnetic ordering at 2 K which is consistent with spin glass behavior. The factors governing the observed structural and magnetic properties of Sr₂MnSbO₆ are discussed and compared with those of other quaternary Mn- and Sb-containing perovskites. Graphs of the temperature of magnetic phase transitions as functions of the cation size were constructed and are discussed for the AB³⁺_1/2B⁵⁺_1/2O₃ series with isomorphous substitution of B³⁺ and B⁵⁺ cations. Possible influence of the A-cation sublattice on magnetic properties is also shortly considered.     

Enhancement of thermoelectric figure of merit by doping Dy in La0.1Sr0.9TiO3 ceramic

Ceramic samples of La_0.1Sr_0.9−xDy_xTiO₃ (x = 0.01, 0.03, 0.07, 0.10) have been prepared by the solid-state reaction method. Characterization from the powder X-ray diffraction indicates that their crystal structure changes from cubic to tetragonal phase. Their electrical and thermal transport properties are measured in the temperature range of 300-1100 K. n-Type thermoelectric is obtained with large Seebeck coefficient. The figure of merit is markedly improved, due to relatively lower electrical resistivity and thermal conductivity by Dy doping effect. A much lower electrical resistivity of 0.8 mΩ cm at room temperature is obtained in La_0.1Sr_0.8Dy_0.1TiO₃, and with a relatively lower thermal conductivity of 2.5 W/m K at 1075 K. The maximum figure of merit reaches ∼0.36 at 1045 K for La_0.1Sr_0.83Dy_0.07TiO₃, which is the largest value among n-type oxide thermoelectric ceramics.     

Oxygen treatment effects on properties of MgO thin films grown on single-crystalline diamond (1 0 0)

Oxygen post-treatment effects on the electronic structure and electrical properties of MgO films grown on homoepitaxial single-crystalline (1 0 0) diamond have been studied. MgO films examined were deposited at room temperature (RT) using an electron beam evaporator and were subsequently either annealed at 573-773 K for 12 h in oxygen ambient or treated by O₂ plasma for 10-40 min. RT resistivities remarkably increased after the O₂ annealing and plasma treatment, indicating that the post treatments play an essential part on the formation and positioning of bandgap states. Cathodoluminescence (CL) spectra had a broad band feature in a wavelength region from 360 to 530 nm, which were decomposed to several peaks originating mainly from the oxygen-vacancy-related F and F⁺ centers and the interstitial vacancies of MgO film. A prominent rectifying behavior of I-V property was observed for a Au/MgO/p-diamond layered structure. Based on temperature dependences of the electrical properties in a temperature region from RT to 600 K, the electrical conduction mechanism in the MgO films is discussed in relation to polaron-related conduction as well as the ionic conduction.     

Synthesis and electrical properties of cubic NaxWO3 thin films across the metal-insulator transition

Highly oriented (1 0 0) Na_xWO₃ thin films were fabricated in the composition range 0.1 ≤ x ≤ 0.46 by pulsed laser deposition technique. The films showed transition from metallic to insulating behaviour at a critical composition between x = 0.15 and 0.2. The pseudo-cubic symmetry of Na_xWO₃ thin films across the transition region is desirable for understanding the composition controlled metal-insulator transition in the absence of any structural phase transformation. The electrical transport properties exhibited by these films across the transition regime were investigated. While the resistivity varied as T² at low temperatures in the metallic regime, a variable range hopping conduction was observed for the insulating samples. For metallic compositions, a non-linear dependence of resistivity in temperature was also observed from 300 to 7 K, whose exponent varied with the composition of the film.     

Crystal structure and superconductivity of rubidium tungsten bronzes RbxWO3 prepared by a hybrid microwave method

The rubidium tungsten bronzes Rb_xWO₃ have been prepared from Rb₂CO₃, WO₃ and W powders using hybrid microwave method. The single hexagonal phase samples can be obtained as actual rubidium content x in the range of 0.21-0.33, and their lattice parameters a and c linearly drop and rise with the increase of rubidium content respectively. For samples with x = 0.14, 0.16, 0.18, the superconducting transition temperature T_c from resistivity measurements does not change with the rubidium content, while T_c from susceptibility measurements shows a decrease from 5.3 K for x = 0.14 to 4.8 K for x = 0.18. The charge density wave (CDW) transition appears in Rb_0.21WO₃, Rb_0.23WO₃ and Rb_0.25WO₃ at about 200-260 K. The CDW transition is most obvious in Rb_0.23WO₃ which shows the lowest degree of crystallization among the samples.     

Hygroscopicity and bulk thermal expansion in Y2W3O12

Negative thermal expansion material, Y₂W₃O₁₂ has been synthesized by the solid-state method and bulk thermal expansion of the material has been investigated from 300 to 1100 K. The material reversibly forms a trihydrate composition whose X-ray diffraction pattern can be indexed to an orthorhombic unit cell with a = 10.098(1) Å, b = 13.315(3) Å, c = 9.691(4) Å. The cell volume of the hydrated pattern is 7% smaller than the unhydrated cell volume. According to the dilatometric studies, the material shows a 3-6% increase in the linear strain at about 400 K, which can be attributed to the removal of water. Sintering the material at 1473 K leads to large grain size of >100 μm, which results in a large hysteresis in the bulk thermal expansion behavior. Hot pressing at 1273 K under a uniaxial pressure of 25 MPa results in a fine-grained (2-5 μm) ceramic. Glazing the ceramic prevents moisture pick up and a linear thermal expansion over the entire temperature range 1100-300 K and an average linear thermal expansion co-efficient of −9.65 × 10⁻⁶/K is observed. The effect of water on the thermal expansion behavior of this system is discussed.     

Synthesis and characterization of K2NiF4-type CaLnCoO4 (Ln = Sm and Gd)

K₂NiF₄-type CaLnCoO₄ (Ln = Sm and Gd) has been synthesized at 1173 or 1223 K in air using citric acid (CA) and ethylene glycol (EG). CaLnCoO₄ (Ln = Sm and Gd) has an orthorhombic structure with the space group Bmab. The average particle sizes are approximately 300 nm for CaSmCoO₄ and approximately 170 nm for CaGdCoO₄, respectively. The global instability index (GII) indicates that the crystal structure of CaGdCoO₄ is more stable than that of CaSmCoO₄. CaLnCoO₄ (Ln = Sm and Gd) is a p-type semiconductor and shows paramagnetic behavior above 5 K. The 1/χ-T curve of CaSmCoO₄ deviates from the Curie-Weiss law, whereas the 1/χ-T curve of CaGdCoO₄ follows the Curie-Weiss law in the temperature range of 5 ≤ T ≤ 300 K. From the values of the observed effective magnetic moment (μ_eff) of CaLnCoO₄ (Ln = Sm and Gd), it is considered that the spin state of the Co³⁺ ion is low.     

Lattice thermal expansion studies of V2GeO4F2: A topaz type oxide-fluoride

A new compound V₂GeO₄F₂ was earlier found to exist in the V₂O₃-VF₃-GeO₂ system and the structure elucidation revealed it to be iso-structural to the mineral topaz. Herein, we report the lattice thermal expansion data of this compound. The lattice thermal expansion of V₂GeO₄F₂ was studied in the temperature range of 298-873 K under a flowing helium atmosphere by the high temperature XRD (HTXRD). The coefficients of axial thermal expansions of V₂GeO₄F₂ were found to be as: α_a = 3.5 × 10⁻⁶, α_b = 6.1 × 10⁻⁶ and α_c = 7.6 × 10⁻⁶ K⁻¹. The coefficient of volume (α_V) thermal expansion was 17.3 × 10⁻⁶ K⁻¹, which is relatively low compared to many analogues silicates.     

Synthesis and properties of GeS2-Ga2S3-PbI2 chalcohalide glasses

The glass-forming region in the GeS₂-Ga₂S₃-PbI₂ system was determined and the basic parameters of thermal and optical properties (glass transition temperature, density, microhardness and transmission window) for these glasses have been measured. Better thermal stability originated from their larger difference between T_x and T_g in the range of 107-161 °C, higher glass transition temperatures between 252 and 398 °C and wide optical transmission window from 0.5 to 12.7 μm make these glasses the promising candidate materials for rare earth doped fiber amplifiers and nonlinear optical devices.     

Preparation and characterisation of La10−xGe5.5Al0.5O26±δ apatites by freeze-drying precursor method

Nanocrystalline powders of La_10−xGe_5.5Al_0.5O_26±δ (x = 0-0.5) with an average crystallite size of 50 nm were prepared by a freeze-drying precursor method. These powders were used to obtain dense ceramic materials at rather low temperature as 1100-1200 °C for 1 h and to study the transport properties by impedance spectroscopy. The composition with the highest La-content (x = 0) exhibits a second-order phase transition from triclinic () to hexagonal (P6₃/m) space groups around 750 °C, whereas for x ≥ 0.2 the materials presents hexagonal structure in the whole temperature range studied. The thermal properties of these materials were investigated by high temperature X-ray diffraction (XRD), thermal analysis (TG/DTA) and impedance spectroscopy. These results confirmed the incorporation of water in the germanate-apatite structure. However, the conductivity resulted to be independent on the gas atmosphere used, which seems to indicate that the proton contribution to the overall conductivity is negligible in these materials.     

A quaternary lead based perovskite structured materials with diffuse phase transition behavior

A lead based quaternary compound composed of 0.25(PbZr_0.52Ti_0.48O₃) + 0.25(PbFe_0.5Ta_0.5O₃) + 0.25 (PbF_0.67W_0.33O₃) + 0.25(PbFe_0.5Nb_0.5O₃) - (PZT-PFT-PFW-PFN) was synthesized by conventional solid-state reaction techniques. It showed moderate high dielectric constant, low dielectric loss, and two diffuse phase transitions, one below the room temperature ∼261 K and other above ∼410 K. X-ray diffraction (XRD) patterns revealed a tetragonal crystal structure at room temperature where as scanning electron micrograph (SEM) indicates inhomogeneous surface with an average grain size of 500 nm-3 μm. Well saturated ferroelectric hysteresis loops with good saturation polarization (spontaneous polarization, P_s ∼ 30.68 μC/cm²) were observed. Temperature-dependent ac conductivity displayed low conductivity with kink in spectra near the phase transition. In continuing search for developing new ferroelectric materials, in the present study we report stoichiometric compositions of complex perovskite ceramic materials: (PZT-PFT-PFW-PFN) with diffuse phase transition behavior. The crystal structure, dielectric properties, and ferroelectric properties were characterized by XRD, SEM, dielectric spectroscopy, and polarization. 1/? versus (T) plots revealed diffuse relaxor phase transition (DPT) behavior. The compositional variation on the phase transition temperature, dielectric constant, and ferroelectric to paraelectric phase transitions are discussed.     

Structure and properties of ternary manganese nitride Mn3CuNy thin films fabricated by facing target magnetron sputtering

Deposition of Mn₃CuN_y thin films on single crystal Si (1 0 0) at various substrate temperatures (T_sub) by facing target magnetron sputtering is reported. The crystal structure and composition were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results confirmed that the crystalline antiperovskite Mn₃CuN_y thin film with (2 0 0) highly preferred texture had been obtained at T_sub = 180 °C. Furthermore, for the resulting Mn₃CuN_y thin film, it showed different properties compared with the bulk counterpart. There was a paramagnetic to ferrimagnetic transition at 225 K with decreasing temperature. The change of the lattice constant with temperature presented positive thermal expansion behavior and no structural transition was observed. The average linear thermal expansion coefficient (α) is 2.49 × 10⁻⁵ K⁻¹ from 123 K to 298 K. More interestingly, the temperature dependence of resistivity displayed a semiconductor-like behavior, i.e. an obvious monotonous decrease of resistivity with increasing temperature.     

Modification of the physical properties of semiconducting MgAl2O4 by doping with a binary mixture of Co and Zn ions

The effects of doping of MgAl₂O₄ by a binary mixture of Co and Zn ions on the absorbance, electrical resistivity, capacitance, thermal conductivity, heat capacity and thermal diffusivity are reported in this paper. The materials with the nominal composition Mg_1−2x(Co,Zn)_xAl₂O₄ (x = 0.0-0.5) are synthesized by solution combustion synthesis assisted by microwave irradiation. The substituted spinels are produced with a Scherrer crystallite size of 18-23 nm, as opposed to 45 nm for undoped samples, indicated by X-ray diffraction and confirmed by transmission electron microscopy. These materials also show better thermal stability in the temperature range of 298-1773 K. Three strong absorption bands at 536, 577 and 630 nm are observed for the doped samples which are attributed to the three spin allowed (⁴A₂ (F) → ⁴T₁ (P)) electronic transitions of Co²⁺ at tetrahedral lattice sites while pure magnesium aluminate remains transparent in the whole spectral range. The semiconducting behavior of the materials is evident from the temperature dependence of the electrical resistivity. Resistivity and activation energy are higher for the substituted samples. Fitting of the resistivity data is achieved according to the hopping polaron model of solids. Both dielectric constant and loss increase on account of doping. The dielectric data are explained on the basis of space charge polarization. The thermal conductivity and diffusivity are lowered and the heat capacity is increased in the doped materials. Wiedemann-Franz's law is used to compute the electronic and lattice contributions towards the total thermal conductivity.     

Influences of poling condition and sintering temperature on piezoelectric properties of (Na0.5Bi0.5)1 − xBaxTiO3 ceramics

The structure, ferroelectric characteristics and piezoelectric properties of (Na_0.5Bi_0.5)_1 − xBa_xTiO₃ (x = 0.04, 0.06, 0.10) ceramics prepared by conventional solid state method were investigated. The influences of poling condition and sintering temperature on the piezoelectric properties of the ceramics were examined. The piezoelectric properties of the ceramics highly depend on poling field and temperature, while no remarkable effect of poling time on the piezoelectric properties was found in the range of 5-25 min. Compared with (Na_0.5Bi_0.5)_0.96Ba_0.04TiO₃ and (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃, the piezoelectric properties of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ are more sensitive to poling temperature due to the relatively low depolarization temperature. Moderate increase of sintering temperature improved the poling process and piezoelectric properties due to the development of microstructural densification and crystal structure. With respect to sintering behavior and piezoelectric properties, a sintering temperature range of 1130-1160 °C was ascertained for (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃.     

Crystal structure, magnetic and thermal properties of LaFeTeO6

LaFeTeO₆ was prepared by solid state reaction of La₂O₃, Fe₂O₃ and TeO₂ in 1:1:2 molar ratios and characterized by powder X-ray diffraction, thermogravimetry and magnetometry. The detailed crystal structure analysis was carried out by Rietveld refinement. LaFeTeO₆ crystallizes in a trigonal lattice with unit cell parameters: a = 5.2049(1) Å and c = 10.3457(2) Å, V = 242.73(2) Å³. The crystal structure is built from sheets of the edge shared FeO₆ and TeO₆ octahedra stacked along the c-axis. These sheets are connected together by La³⁺ ions. Thermogravimetric analysis of the compound showed it to be thermally stable up to 1323 K and continuous loss of TeO₂ was observed above 1323 K leading to the formation of LaFeO₃. High temperature XRD studies revealed a normal expansion behavior of the compound. Temperature and field dependent magnetization of LaFeTeO₆ showed paramagnetic behavior in the temperature range of 3-300 K. The effective magnetic moment per Fe³⁺ ion (5.14 μB) indicates the high spin d⁵ state of Fe³⁺ ion.     

High-temperature anomalies of dielectric constant in TiO2 thin films

Anatase and rutile TiO₂ thin films were prepared by chemical vapor deposition with precursors Ti(OPrⁱ)₄ and Ti(dpm)₂(OPrⁱ)₂ (dpm = 2,2,6,6-tetramethylheptane-3,5-dione and Prⁱ = isopropyl), respectively. The dielectric properties of TiO₂ thin films have been studied in 20-1100 K temperature range in air, in controlled Ar/O₂ atmospheres, and in vacuum with silicon-based metal-insulator-semiconductor Au/TiO₂/Si capacitors. High-temperature (T_c ∼ 980 K) anomalous behavior of dielectric constant was observed in both anatase and rutile TiO₂ thin films.     

Specific heat, electrical resistivity and thermoelectric power of YbNi4Si

The studies of the specific heat, electrical resistivity and thermoelectric power of YbNi₄Si are reported. These studies are supported by magnetic susceptibility and X-ray photoemission spectroscopy (XPS) measurements. YbNi₄Si does not order magnetically down to 4 K. Nearly in the whole temperature range studied the magnetic susceptibility follows a Curie law with μ_eff = 4.15 μ_B/f.u. This effective magnetic moment is close to the value expected for the 4f¹³ configuration (4.54 μ_B). The Yb²⁺ and Yb³⁺ peaks observed by XPS in the valence band region confirm the domination of the Yb³⁺ valence state. Based on the specific heat measurements, the electronic specific heat coefficient γ = 25 mJ/mol/K² and the Debye temperature θ_D = 320 K were derived. A quadratic dependence of electrical resistivity at low temperatures has been observed. The Kadowaki-Woods ratio has been discussed. The thermoelectric power has been analyzed in the framework of the two band model.