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.     

Effect of Zn substitution for Co on the transport properties of Y BaCo4O7

Electrical resistivity and Seebeck coefficients of Y BaCo_4−xZn_xO₇ (x=0.0,0.5,1.0,2.0) were investigated in the temperature range 350-1000 K. It was found that the electrical resistivity and activation energy increase with increasing Zn concentration, while Seebeck coefficients do not increase but decrease when electrical resistivity increases. We explained the increase of electrical resistivity and the drop of Seebeck coefficients for Zn-substituted samples by the decrease of carrier mobility, rather than of carrier concentration. The effect of oxygen absorption and desorption on the electrical resistivity and Seebeck coefficients was also investigated. An abrupt change of transport properties happens at about 650 K for x=0.0 and 0.5 samples measured in oxygen. For x=1.0 and 2.0 samples, however, such change disappears and the transport behavior in oxygen is almost same as that in nitrogen due to the significant suppression of oxygen diffusion caused by the higher Zn concentration in these samples.     

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.     

Crystallization-dependent magnetic properties of Mn1.56Co0.96Ni0.48O4 thin films

The effects of magnetic property dependence of the Mn_1.56Co_0.96Ni_0.48O₄ (MCN) films on crystallization are investigated in the growth temperature of 450-750 °C. With the growth temperature increase, both the crystalline quality and the grain size improve. The MCN films exhibit paramagnetic to ferromagnetic transition and the paramagnetic parts fit to the modified Curie-Weiss law. The ferromagnetic couplings of the magnetic ions in the MCN films enhance at elevated growth temperature. The saturation magnetization at 5 K increases with increasing growth temperature, but coercive field decreases monotonously. The magnetic properties of the MCN films strongly depend on their microstructures.     

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.     

Structural and transport properties of cubic spinel ZnCo2O4 thin films grown by reactive magnetron sputtering

We report on the growth of cubic spinel ZnCo₂O₄ thin films by reactive magnetron sputtering and bipolarity of their conduction type by tuning of oxygen partial pressure ratio in the sputtering gas mixture. Crystal structure of zinc cobalt oxide films sputtered in an oxygen partial pressure ratio of 90% was found to change from wurtzite Zn_1−xCo_xO to spinel ZnCo₂O₄ with an increase of the sputtering power ratio between the Co and Zn metal targets, D_Co/D_Zn, from 0.1 to 2.2. For a fixed D_Co/D_Zn of 2.0 yielding single-phase spinel ZnCo₂O₄ films, the conduction type was found to be dependent on the oxygen partial pressure ratio: n-type and p-type for the oxygen partial pressure ratio below ∼70% and above ∼85%, respectively. The electron and hole concentrations for the ZnCo₂O₄ films at 300 K were as high as 1.37×10²⁰ and 2.81×10²⁰ cm⁻³, respectively, with a mobility of more than 0.2 cm²/V s and a conductivity of more than 1.8 S cm⁻¹.     

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.     

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.     

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.     

Conduction behaviour and thermoelectric power of Agx (As0.4Se0.6) 100−x chalcogenide system

Chalcogenide bulk alloys of Ag_x (As_0.4Se_0.6) _100−x (x=5, 7.5, 10, 12.5, 15 and 17.5) system were prepared by the conventional melt-quench technique. The d.c. electrical conductivity (σ) and thermoelectric power (TEP) measurements were carried out in the temperature range from 83 to 373 K and from 253 to 373 K, respectively. Variations of both σ and TEP with ambient temperature proved the p-type semiconducting behaviour of these materials. The current density-electric field characteristics were found to be linear. The activation energies, calculated from both the electrical conductivity E_σ and thermoelectric power E_s, were found to be dependent on composition.     

Low temperature electrical transport in Ag substituted LaMnO3 polycrystalline pellets prepared by a pyrophoric method

A detailed investigation of the electrical resistivity of a series of monovalent (Ag) doped polycrystalline La_1−xAg_xMnO₃ pellets with x ranging from 0.05 to 0.30 and measured over the temperature range between 10 and 350 K is reported. La_1−xAg_xMnO₃ compounds have been prepared by a novel pyrophoric technique. XRD analysis of our samples indicates single phasic nature for samples with Ag content ≤0.15, while samples with higher Ag content (x≥0.2) show presence of both magnetic perovskite and non-magnetic Ag phases. A sharp insulator-metal transition with T_MI close to room temperature arising out of the paramagnetic to ferromagnetic transition, and a large magneto-resistance (MR=∼16%) near T_MI has been observed for all the Ag doped samples. Between T_C(T_p1) and 350 K, all the samples show activated conduction following the Emin-Holstein theory of adiabatic small polaron hopping, while at lower temperatures, in the ferromagnetic regime resistivity appears to be governed by various electron scattering processes. Between 20 and 50 K, a distinct minimum for both H=0 and has been observed, which is explained in terms of inelastic scattering and electron-electron interactions.     

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.     

Synthesis and properties of Mn1−XFeXS single-crystals at room temperature

Results of the first synthesis of Mn_1−XFe_XS single-crystals and its structural, electrical and magnetic properties at room temperature are presented. The Mn²⁺→Fe²⁺ substitution in Mn_1−XFe_XS solid solutions is accompanied by a compression of the NaCl lattice and a small deformation of the octahedral environments, and the concentration transition from dielectric to semimetal. Single-line Mossbauer spectra indicate the paramagnetic state Mn_1−XFe_XS sulfides at room temperature.     

Anomalous magnetism in three-dimensional orthogonal dimer lattice system: (Ba1−xSrx)2Ru3O9 (x≈0.35)

The magnetic and transport properties of a new cubic KSbO₃-type ruthenate, (Ba_1−xSr_x)₂Ru₃O₉ (x≈0.35), have been investigated. The crystal structure has a singular geometry in which ruthenium atoms form an ideal three-dimensional orthogonal dimer lattice. The magnetic susceptibility is Pauli-paramagnetic but exhibits an anomalous temperature dependence reminiscent of a gap-like behavior. The resistivity exhibits a metallic behavior, except for a rise at low temperature.     

Thermoelectric properties of the Bi2−xYxRu2O7 (x=0-2) pyrochlores

Electrical conductivity and Seebeck coefficient for the Bi_2−xY_xRu₂O₇ pyrochlores with x=0.0,0.5,1.0,1.5,2.0 were measured in the temperature range of 473-1073 K in air. With increasing Bi content, the temperature dependence of the electrical conductivity changed from semiconducting to metallic. The signs of the Seebeck coefficient were positive in the measured temperature range for all the samples, indicating that the major carriers were holes. The temperature dependence of the Seebeck coefficient for the Y₂Ru₂O₇ indicated the thermal activation-type behavior of the holes, while that for the Bi_2−xY_xRu₂O₇ with x=0.0-1.5 indicated the itinerant behavior of the holes. The change in the conduction behavior from semiconductor to metal with increasing Bi content is consistent with the increase in the overlap between the Ru4d t_2g and O2p orbitals, but the mixing of Bi6s, 6p states at E_F may not be ruled out. The thermoelectric power factors for the Bi_2−xY_xRu₂O₇ with x=1.5 and 2.0 were lower than 10⁻⁵ W m⁻¹ K⁻² and those with x=0.0,0.5,1.0 were around 1-3×10⁻⁵ W m⁻¹ K⁻².     

Effect of Ti doping on the electrical transport and magnetic properties of layered compound Na0.8CoO2

Effect of Ti doping on the electrical transport and magnetic properties of layered Na_0.8Co_1−xTi_xO₂ compounds has been investigated. The lattice parameters a and c increase with x. A minor amount of Ti doping results in a metal-insulator transition at low temperatures. For samples with x>0.03, the variable-range hopping process dominates the transport behavior above a certain temperature. The temperature dependence of magnetization of all the samples is found to obey the Curie-Weiss law. The mechanism of the doping effect is discussed.     

Effect of cation distribution on the properties of Mn0.2ZnxNi0.8−xFe2O4

Mn_0.2Zn_xNi_0.8−xFe₂O₄ (x=0.2, 0.3, 0.4, 0.5, 0.6) are synthesized by the citrate precursor method. Effects of zinc substitution on DC resistivity, dielectric relaxation intensity, initial permeability, saturation magnetization and Curie temperature have been investigated. It is observed that resistivity increases with increase in zinc concentration up to x=0.5 and then decreases. The observed behaviour is explained in terms of hopping and site preference of ions in the lattice. The main contribution to dielectric relaxation intensity is observed to be due to space charge polarization. Initial permeability is observed to increase with increase in zinc concentration. Saturation magnetization increases up to x=0.4 and then starts decreasing. Canting effect is observed for higher zinc concentrations.     

Small polaron migration in LixMn2O4: From first principles calculations

Migration of small polarons in λ-MnO₂, Li_0.5Mn₂O₄ and LiMn₂O₄ is studied via first principles calculations. Migration energy barriers of single small polaron migrations in λ-MnO₂, Li_0.5Mn₂O₄ and LiMn₂O₄ are 0.22 eV, 0.45 eV and 0.35 eV, respectively. The energy level changes of Mn-3d states along the polaron migration path are analyzed in detail. Results indicate that the activation energy barrier of polaron migration is strongly associated with the energy level shift of Mn-3dz² orbital, which is dependent on the short range structural arrangement of Mn³⁺/Mn⁴⁺ in the crystal. The electrical conduction properties of Li_xMn₂O₄ at room temperature are then discussed.     

X-ray photoelectron spectroscopy study and thermoelectric properties of Al-doped ZnO thin films

In this paper, high quality Al-doped ZnO (AZO) thin films were prepared by direct current (DC) reactive magnetron sputtering using a Zn target (99.99%) containing Al of 1.5 wt.%. The films obtained were characterized by X-ray photoelectron spectroscopy (XPS) and thermoelectric measurements. The XPS results reveal that Zn and Al exist only in oxidized state, while there are dominant crystal lattice and rare adsorbed oxygen for O in the annealed AZO thin films. The studies of thermoelectric property show a striking thermoelectric effect in the AZO thin films. On the one hand, the thermoelectromotive and magnetothermoelectromotive forces increase linearly with increasing temperature difference (ΔT). On the other hand, the thermoelectric power (TEP) decreases with the electrical resistance of the sample. But the TEP increases with the increase of temperature below 300 K, and it nearly does not change around room temperature. The experimental results also demonstrate that the annealing treatment increases TEP, while the external magnetic field degrades TEP.