Influence of Mn-site doped with Ru on the high-temperature thermoelectric performance of CaMnO3−δ

Thermoelectric properties were measured from room temperature to 1000 K to study the effects of doping of Ru for Mn-site on the thermoelectric performance of CaMnO_3−δ. The electrical resistivity shows a sharp decrease upon Ru doping. The Seebeck coefficients of all the samples are negative, and their absolute values remain fairly large even after Ru doping. Among the samples of CaMn_1−xRu_xO_3−δ (x=0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.15, 0.18), CaMn_0.96Ru_0.04O_3−δ has the largest power factor, 1.85×10⁻⁴ W/mK² at 1000 K. An increase or a decrease of x value results in a marked decrease of the power factor. The thermal conductivity and the figure of merit Z of CaMn_0.96Ru_0.04O_3−δ is 2.88 W/mK and 0.64×10⁻⁴ K⁻¹ at 1000 K, respectively.     

Effect of Nb substitution on the structural, dielectric and magnetic properties of multiferroic BiFe1−xNbxO3 ceramics

Polycrystalline BiFe_1−xNb_xO₃ ceramics have been synthesized by standard solid-state reaction method. The effect of Nb substitution on the dielectric, magnetic and magnetoelectric properties of the BiFeO₃ multiferroic perovskite was studied. X-ray diffraction pattern revealed that all the samples with x = 0.00-0.10 showed rhombohedral perovskite structure. We obtained single phase upto doping concentration of x = 0.05 and with further increase in Nb concentration, some impurity peaks appeared. An anomaly in the dielectric constant (?) and dielectric loss (tan (δ)) in the vicinity of the antiferromagnetic Néel temperature (T_N) was observed. Nb substitution reduced the antiferromagnetic Néel temperature (T_N) in BiFe_1−xNb_xO₃. Proper amount of Nb could decrease the dielectric loss. Magnetic hysteresis loops measured at 5 K/300 K and temperature dependent magnetization curves indicated ferromagnetism in Nb substituted BiFeO₃ ceramics. The room temperature magnetic moment was found to increase with increase in Nb concentration. The dependence of dielectric constant on the magnetic field is an evidence of magnetoelectric coupling in BiFe_1−xNb_xO₃ ceramics.     

Synthesis, low-temperature sintering and the dielectric properties of the ZnO-(1 − x)TiO2-xSnO2 (x = 0.04-0.2)

ZnO-(1 − x)TiO₂-xSnO₂ (x = 0.04-0.2) ceramics were prepared by conventional mixed-oxide method combined with a chemical processing. Fine particle powders were prepared by chemical processing to activate the formation of compound and to improve the sinterability. One wt.% of V₂O₅ and B₂O₃ with the mole ratios of 3:1 were used to lower the sintering temperature of ceramics. The effect of Sn content on phase structure and dielectric properties were investigated. The results show that the substituting Sn for Ti accelerates the hexagonal phase transition to cubic phase, and an inverse spinel structure Zn₂(Ti_1−xSn_x)O₄ solid solution forms. The best dielectric properties obtained at x = 0.12. The ZnO-0.88TiO₂-0.12SnO₂ ceramics sintered at 900 °C exhibit a good dielectric property: ?_r = 29 and tan δ = 9.86 × 10⁻⁵. Due to their good dielectric properties, low firing characteristics, ZnO-(1 − x)TiO₂-xSnO₂ (x = 0.04-0.2) can serve as the promising microwave dielectric capacitor.     

Improved hydrogen evolution activities under visible light irradiation over NaTaO3 codoped with lanthanum and chromium

Na_1−xLa_xTa_1−xCr_xO₃ and NaTa_1−xCr_xO₃ (x = 0.01, 0.03, 0.05 and 0.10) have been synthesized by a solid state reaction method. These photocatalysts can produce H₂ in the presence of methanol under visible light irradiation (λ > 420 nm). The photocatalytic activities of Na_1−xLa_xTa_1−xCr_xO₃ are much higher than those of NaTa_1−xCr_xO₃, respectively. Especially, the H₂ evolution rate of Na_0.9La_0.1Ta_0.9Cr_0.1O₃ is 2.2 μmol h⁻¹, which is nearly 4 times higher than that of NaTa_0.9Cr_0.1O₃ (0.6 μmol h⁻¹). The improved activities of Na_1−xLa_xTa_1−xCr_xO₃ compared with NaTa_1−xCr_xO₃ can be ascribed to two factors: one is smaller particle size and higher specific surface area which is caused by the doping of lanthanum; the other is that Na_1−xLa_xTa_1−xCr_xO₃ has less Cr⁶⁺, which is induced by codoping of lanthanum and chromium.     

Dielectric properties of Ba(Ti1 − xZrx)O3 solid solutions

This paper reports the structural and dielectric properties of Ba(Ti_1 − xZr_x)O₃ (x = 0-0.3) ceramics. Single-phase solid solutions of the samples were determined by X-ray diffraction. Microscopic observation by scanning electron microscope revealed dense, single-phase microstructure with large grains (20-60 μm). The evolution of dielectric behavior from a sharp ferroelectric peak (for x ≤ 0.08) to a round dielectric peak (for 0.15 ≤ x ≤ 0.25) with pinched phase transitions and successively to a ferroelectric relaxor (for x = 0.3) was observed with increasing Zr concentration. Compared with pure BaTiO₃, broaden dielectric peaks with high dielectric constant of 25,000-40,000 and reasonably low loss (tanδ: 0.01-0.06) in the Ba(Ti_1 − xZr_x)O₃ ceramics have been observed, indicating great application potential as a dielectric material.     

Influence of Cr deficiency on sintering character and properties of SOFC interconnect material La0.7Ca0.3Cr1−xO3−δ

The SOFC interconnect materials La_0.7Ca_0.3Cr_1−xO_3−δ (x = 0-0.09) were prepared using an auto-ignition process and characterized. XRD analysis indicated that all the samples displayed a pure perovskite phase after sintered at 1400 °C for 4 h. The relative density increased from 67% (x = 0) to 95.8% (x = 0.02) and reached to about 97% (x > 0.02), as sintered at 1400 °C for 4 h. The electrical conductivity in air dramatically increased and then lowered slowly with x values. The sample with 0.03 Cr deficiency got a maximum conductivity of 61.7 S cm⁻¹ at 850 °C in air, which is about three times as high as that of the sample with no Cr deficiency (20.6 S cm⁻¹). The sample with 0.06 Cr deficiency exhibited the highest electrical conductivity of 3.9 S cm⁻¹ at 850 °C in pure H₂. The thermal expansion coefficient (TEC) were below 11.8 × 10⁻⁶ K⁻¹ for samples of x = 0.02-0.09, that was of well compatibility with other components in SOFCs. Results indicate that the materials with 0.02-0.06 Cr deficiency have high properties and are much suitable for SOFC interconnect.     

Effect of BiFeO3 additions on the dielectric and piezoelectric properties of (K0.44Na0.52Li0.04)(Nb0.84Ta0.1Sb0.06)O3 ceramics

(1 − x) (K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.1Sb_0.06)O₃ − x BiFeO₃ (x = 0, 0.002, 0.004, 0.006, 0.008, 0.01) lead-free piezoelectric ceramics were prepared by the conventional ceramic processing. The compositional dependence of the phase structure and the electrical properties of the ceramics were studied. A morphotropic phase boundary between the orthorhombic and tetragonal phases was identified in the composition range of 0.004 < x < 0.006. The ceramics near the morphotropic phase boundary exhibit a strong compositional dependence and enhanced piezoelectric properties. The ceramics with 0.6 mol.% BiFeO₃ exhibit good electrical properties (d₃₃ ∼ 246 pC/N, k_p ∼ 43%, T_c ∼ 285 °C, ?_r ∼ 1871, and tan δ ∼ 1.96%). These results show that the (1 − x) (K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.1Sb_0.06)O₃ − x BiFeO₃ ceramic is a promising lead-free piezoelectric material for applications in different devices.     

Y0.08Sr0.92FexTi1−xO3−δ perovskite for solid oxide fuel cell anodes

A single phase perovskite Y_0.08Sr_0.92Fe_xTi_1−xO_3−δ (x = 0.05, 0.1,0 0.20, 0.25, 0.40, and 0.50) was fabricated at 1400 °C in air by a solid state reaction method and its electrical conductivity and electrochemical properties as an anode were investigated as a function of the Fe content. Doping with Y for Sr allowed the SrFe_xTi_1−xO_3−δ perovskite to be stable at 800 °C in a reducing atmosphere. At 900 °C, metallic Fe precipitated and the stability of the perovskite phase under a reducing atmosphere decreased as the Fe content increased. The conductivity of Y_0.08Sr_0.92Fe_xTi_1−xO_3−δ (x = 0.40) was greater than that of the x = 0.20 sample. The conductivity of Y_0.08Sr_0.92Fe_xTi_1−xO_3−δ was found to be 2 × 10⁻¹ Scm⁻¹ at 800 °C in H₂. Sintering the Y_0.08Sr_0.92Fe_xTi_1−xO_3−δ anode at 1200 °C was found to be optimum to obtain not only good interfacial adhesion, but also a fine grain structure. The Y_0.08Sr_0.92Fe_0.25Ti_0.75O_3−δ anode exhibited the lowest polarization resistance (0.7 and 1.8 Ωcm² at 800 and 700 °C).     

Acceptor doping of Ln2Ti2O7 (Ln = Dy, Ho, Yb) pyrochlores with divalent cations (Mg, Ca, Sr, Zn)

New LANTIOX high-temperature conductors with the pyrochlore structure, (Ln_1−xA_x)₂Ti₂O_7−δ (Ln = Dy, Ho, Yb; A = Ca, Mg, Zn; x = 0, 0.01, 0.02, 0.04, 0.07, 0.1), have been prepared at 1400-1600 °C using mechanical activation, co-precipitation and solid-state reactions. Acceptor doping in the lanthanide sublattice of Ln₂Ti₂O₇ (Ln = Dy, Ho, Yb) with Ca²⁺, Mg²⁺ and Zn²⁺ increases the conductivity of the titanates except in the (Ho_1−xCa_x)₂Ti₂O_7−δ system, where the conductivity decreases slightly at low doping levels, x = 0.01-0.02. The highest conductivity in the (Ln_1−xA_x)₂Ti₂O_7−δ (Ln = Dy, Ho, Yb; A = Ca, Mg, Zn) systems is offered by the (Ln_0.9A_0.1)₂Ti₂O_7−δ and attains maximum value for (Yb_0.9Ca_0.1)₂Ti₂O_6.9 and (Yb_0.9Mg_0.1)₂Ti₂O_6.9 solid solutions:∼2 × 10⁻² and 9 × 10⁻³ S cm⁻¹ at 750 °C, respectively. Ca and Mg are best dopants for Ln₂Ti₂O₇ (Ln = Dy, Ho, Yb) pyrochlores. Using impedance spectroscopy data, we have determined the activation energies for bulk and grain-boundary conduction in most of the (Ln_1−xA_x)₂Ti₂O_7−δ (Ln = Dy, Ho; A = Ca, Mg, Zn) materials. The values obtained, 0.7-1.05 and 1-1.4 eV, respectively, are typical of oxygen ion conductors. We have also evaluated defect formation energies in the systems studied.     

Studying trivalent/bivalent metal ion doped TiO2 as p-TiO2 in bipolar heterojunction devices

Trivalent/bivalent metal ions doped TiO₂ thin films (M_xTi_1−xO₂, M = Cr³⁺, Fe³⁺, Ni²⁺, Co²⁺, Mn²⁺ and x = 0.01, 0.05, 0.1, 0.15, 0.2) were deposited on Indium–tin oxide (ITO) coated glass substrates by spin coating technique. X-ray photoelectron spectroscopy (XPS) showed Ti⁴⁺ oxidation state of the Ti2p band in the doped p-TiO₂. The homogenous M_xTi_1−xO₂ was used to support n-ZnO thin films with thickness ∼40–80 nm and vertically aligned n-ZnO nanorods (NR) with length ∼300 nm and 1.5 μm. Current (I)–voltage (V) characteristics for the Ag/n-ZnO/M_xTi_1−xO₂/ITO/glass assembly showed rectifying behavior with small turn-on voltages (V₀) < 1 V. The ideality factor (η) and the resistances in both forward and reverse bias were calculated. The temperature dependence performance of these bipolar devices was performed and variation of the parameters with temperature was studied.     

Dielectric properties of sol-gel derived high-k titanium silicate thin films

High-k dielectric titanium silicate (Ti_xSi_1 − xO₂) thin films have been deposited by means of an optimized sol-gel process. At the optimal firing temperature of 600 °C, the Ti_0.5Si_0.5O₂ films are shown to exhibit not only a dielectric constant (k) as high as ∼ 23 but more importantly the lowest leakage current and dielectric losses. Fourier transform infrared spectroscopy shows an absorbance peak at 930 cm^− 1, which is a clear signature of the formation of Ti-O-Si bondings in all the silicate films. The developed sol-gel process offers the required latitude to grow Ti_xSi_1 − xO₂ with any composition (x) in the whole 0 ≤ x ≤ 1 range. Thus, the k value of the Ti_xSi_1 − xO₂ films can be tuned at any value between that of SiO₂ (3.8) to that of TiO₂ (k ∼ 60) by simply controlling the TiO₂ content of the films. The composition dependence of the dielectric constant of the Ti_xSi_1 − xO₂ films is analyzed in the light of existing models for dielectric composites.     

Phase stabilization and microstructural studies of lead lanthanum titanate thin films

Thin ferroelectric films of PLTx (Pb_1−xLa_xTi_1−x/4O₃) have been prepared by a sol-gel spin coating process. As deposited films were thermally treated for crystallization and formation of perovskite structure. Characterization of these films by X-ray diffraction (XRD) have been carried out for various concentrations of La (x = 0.04, 0.08 and 0.12) on ITO coated corning glass substrates. For a better understanding of the crystallization mechanism, the investigations were carried out on films annealed at temperatures (350, 450, 550 and 650 °C). Characterization of these films by X-ray diffraction shows that the films annealed at 650 °C exhibit tetragonal phase with perovskite structure. Atomic force microscope (AFM) images are characterized by slight surface roughness with a uniform crack free, densely packed structure. Fourier transform infrared spectra (FTIR) studies of PLTx thin films (x = 0.08) deposited on Si substrates have been carried out to get more information about the phase stabilization.     

Correlation of crystal structure and microwave dielectric properties for Zn(Ti1−xSnx)Nb2O8 ceramics

The correlation of crystal structure and microwave dielectric properties for Zn(Ti_1−xSn_x)Nb₂O₈ ceramics were investigated. The Zn(Ti_1−xSn_x)Nb₂O₈ ceramics contained ZnTiNb₂O₈ and an unknown Columbite-type phase. The columbite structure phase with increasing degree of ordering led to decrease of dielectric constant, increase of Qf and τ_f. The ZnTiNb₂O₈ with decreasing cation valence led to increase of τ_f. The typical values were: ? = 30.88, Qf = 43,500 GHz, τ_f = −54.32 × 10⁻⁶/ °C.     

Variation in structural,optical and magnetic properties of Zn1−xCrxO (x = 0.0, 0.10, 0.15, and 0.20) nanoparticles: Role of dopant concentration on non-saturation of magnetization

Cr-doped ZnO, i.e. Zn_1−xCr_xO (x = 0.00, 0.05, 0.10, 0.15 and 0.20) nanoparticles were synthesized by sol–gel route. The structural and morphological properties of these nanoparticles were investigated by high resolution transmission electron microscope (HRTEM). The average particle size of Zn_1−xCr_xO nanoparticles decreases from 75 to 40 nm with the increase in x from 0.00 to 0.20. The rings observed in selected area diffraction pattern revealed that up to x = 0.10 these nanoparticles have single phase ZnO. However, a secondary spinel phase of ZnCr₂O₄ was observed for higher Cr doping (x ≥ 0.15). The optical band gap calculated using UV–visible absorption was decreased from 3.27 to 2.27 eV with the increase in Cr-doping from 0.00 to 0.20 in ZnO nanoparticles. The undoped ZnO (Zn_1−xCr_xO; x = 0.00) nanoparticles did not show any hysteresis loop at room temperature, however, clear loops were obtained for x = 0.05–0.20. Additionally, magnetization (M) vs. applied magnetic field (H) loops for lower Cr-concentration (x = 0.05) saturate at 5 kOe, and while those with higher Cr concentration (x > 0.05) do not show saturation even at 10 kOe. This may be attributed to increase in the defects at higher Cr-doping into ZnO. The value of saturation magnetization was found to decrease from 4.24 emu g⁻¹ to 1.96 emu g⁻¹ with the increase in Cr doping from x = 0.05 to 0.20 in ZnO and may be due to the secondary ZnCr₂O₄ phase.     

Study on structural and electrical properties of layered perovskite-type oxide-ion conductor

Samples of BINAVOX (Bi₂Na_xV_1−xO_5.5−2x), in the composition range 0 ≤ x ≤ 0.20 were synthesized by sol–gel citrate route. Thermal decomposition and phase structure were characterized using FT-IR, Powder X-ray diffraction and simultaneous thermogravimetric and differential thermal analysis. It has been found that BINAVOX xerogels are completely calcinated above 550 °C for 3 h of thermal treatments. Furthermore, the highly conducting γ-phase was stabilized for compositions with x ≥ 0.15. AC impedance spectroscopy revealed that the diffusion of oxide-ion vacancies is thermally activated in both grain interiors and boundaries. In general, the relaxation time of grain boundaries contribution is two orders of magnitude higher than that of grain interiors. The dielectric permittivity showed a general decay with the increase in sodium substitution. Importantly, the composition dependence of electrical conductivity exhibited a maximum for x = 0.13 at lower temperatures (σ₃₀₀ ∼ 1.34 × 10⁻⁵ S cm⁻¹), which is attributed to the reduction in the activation energy of conduction.     

Ohmic contacts and n-type doping on TixCr2 − xO3 films and the temperature dependence of their transport properties

A procedure to dope n-type Cr_2 − xTi_xO₃ thin films is proposed. Besides doping the material, at the same time the method forms ohmic contacts on Ti_xCr_2 − xO₃ films. It consists on the deposition of 10 nm Ti and 50 nm Au, followed by thermal annealing at 1000 °C for 20 min in N₂ atmosphere. Ohmic contacts were formed on three samples with different composition: x = 0.17, 0.41 and 1.07 in a van der Pauw geometry for Hall effect measurements. These measurements are done between 35 K and 373 K. All samples showed n-type nature, with a charge carrier density (n) on the order of 10²⁰ cm^− 3, decreasing as x increased. As a function of temperature, n shows a minimum around 150 K, while the mobilities have an almost constant value of 11, 28 and 7 cm²V^− 1 s^− 1 for x = 0.17, 0.41 and 1.07, respectively.     

Study on properties of BaxSmyTi7O20 ceramics with CaO-SiO2-B2O3 glass

The effect of CaO-SiO₂-B₂O₃ (CSB) glass addition on the sintering temperature and dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics has been investigated using X-ray diffraction, scanning electron microscopy and differential thermal analysis. The CSB glass starts to melt at about 970 °C, and a small amount of CSB glass addition to Ba_xSm_yTi₇O₂₀ ceramics can greatly decrease the sintering temperature from about 1350 to about 1260 °C, which is attributed to the formation of liquid phase. It is found that the dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics are dependent on the amount of CSB glass and the microstructures of sintered samples. The product with 5 wt% CSB glass sintered at 1260 °C is optimal in these samples based on the microstructure and the properties of sintering product, when the major phases of this material are BaSm₂Ti₄O₁₂ and BaTi₄O₉. The material possesses excellent dielectric properties: ?_r = 61, tan δ = 1.5 × 10⁻⁴ at 10 GHz, temperature coefficient of dielectric constant is −75 × 10⁻⁶ °C⁻¹.     

Giant pyroelectric coefficient of Mn-doped PLT thin films epitaxially grown on (001) Pt/MgO

The c-axis-oriented epitaxial thin films of Mn-doped Pb_1−xLa_xTi_1−x/4O₃ (PLT) on (001) Pt/MgO substrates were prepared by rf-magnetron sputtering. To investigate the effect of the doped ion, 0-1.7 mol% MnO₂ added to the PLT target powder. The temperature dependence of the relative dielectric constant ?_r measurements and modified Curie-Weiss plots suggested that the increasing of diffuseness n was induced by high-La substitution and the diffuseness n of PLT thin films decreased by the addition of Mn, considerably. Inner stress and thermodynamic analysis were carried out and the results propose that the increasing of γ with Mn doping caused by increasing the misfit strain of the c-axis-oriented epitaxial PLT thin films and substrate. As a result, giant pyroelectric coefficient (γ = 15.8 × 10⁻⁸ C/cm² K) of Mn-doped epitaxial PLT thin film was achieved.     

Novel transparent conducting oxide: Anatase Ti1−xNbxO2

Single-crystalline Ti_1−xNb_xO₂ (x = 0.2) films of 40 nm thickness were deposited on SrTiO₃ (100) substrates by the pulsed laser deposition (PLD) technique. X-ray diffraction measurement confirmed epitaxial growth of anatase (001) film. The resistivity of Ti_1−xNb_xO₂ films with x ≥ 0.03 is 2-3 × 10^− 4 Ω cm at room temperature. The carrier density of Ti_1−xNb_xO₂, which is almost proportional to the Nb concentration, can be controlled in a range of 1 × 10¹⁹ to 2 × 10²¹ cm^− 3. Optical measurements revealed that internal transmittance in the visible and near-infrared region for films with x = 0.03 was more than 97%. These results demonstrate that the presently developed anatase Ti_1−xNb_xO₂ is one of the promising candidates for the practical TCOs.     

Dielectric properties of a new ceramic system (1 − x)Mg4Nb2O9-xCaTiO3 at microwave frequency

The microstructures and the microwave dielectric properties of the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system were investigated. In order to achieve a temperature-stable material, CaTiO₃ (τ_f ∼ 800 ppm/°C) was chosen as a τ_f compensator and added to Mg₄Nb₂O₉ (τ_f ∼ −70 ppm/°C) to form a two phase system. It was confirmed by the XRD and EDX analysis. By appropriately adjusting the x-value in the (1 − x)Mg₄Nb₂O₉-xCaTiO₃ ceramic system, near-zero τ_f value can be achieved. A new microwave dielectric material, 0.5Mg₄Nb₂O₉-0.5CaTiO₃ applicable in microwave devices is suggested and possesses the dielectric properties of a dielectric constant ?_r ∼ 24.8, a Q × f value ∼82,000 GHz (measured at 9.1 GHz) and a τ_f value ∼−0.3 ppm/°C.