Thermoelectric power of CuCrxVySe4 p-type spinel semiconductors

Structural, electrical and magnetic measurements of polycrystalline CuCr_xV_ySe₄ spinels with x=1.79, 1.64 and 1.49 and y=0.08, 0.22 and 0.45, respectively, are presented. The compounds under study crystallize in regular system of a normal spinel type MgAl₂O₄ structure with the space group symmetry Fd3m. The chromium spins are coupled ferromagnetically and show both strong long- and short-range magnetic interactions evidenced by the large values of the Curie (T_C) and Curie–Weiss (θ_CW) temperatures, decreasing from T_C=407 K and θ_CW=415 K for y=0.08, via T_C=349 K and θ_CW=367 K for y=0.22 to T_C=283 K and θ_CW=293 K for y=0.45, respectively. In all the studied spinels a change of the electrical conductivity character from the semiconductive into the metallic one above 230 K was observed. A detailed thermoelectric power analysis showed a domination of diffusion thermopower component, maximum of phonon drag component at 230 K, a decrease of impurity component with increasing V content, as well as the weak magnon excitations at 40 K.     

Structural,electrical and transport phenomena of Co ferrite substituted by Cd

A series of samples of Co_1−xCd_xFe₂O₄ (x=0, 0.1, 0.3, 0.5, 0.7and 0.9) were prepared by the usual ceramic technique and sintered at 1473 K for 6 h. The X-ray analysis shows the existence of single phase spinel structure with the increase of lattice parameter and density with increasing Cd contents whereas the porosity decreases. The DC electrical conductivity increases with increasing temperature. It is also increased by increasing Cd content and reaches maximum at x=0.7 at which the activation energy for conduction becomes minimum. The transition temperature T_c shifts to a higher value as Cd content increases. The thermoelectric power α is converted from a positive value for Co ferrite (hole) to a negative value for the mixed ferrite Co_1−xCd_xFe₂O₄. The activation energy for mobility E_μ is nearly equal to E_σ and the thermoelectric power α is nearly constant with the variation of temperature which make together a strong reason for the presence of hopping condition mechanism.     

Transport studies of YBa2Cu3Oy/YxPr1−xBa2Cu3Oy and YBa2Cu3Oy/R0.7M0–3MnO3 superlattices,in which R=La or Nd,and M=Ca or Sr

We report the transport studies of YBa₂Cu₃O_y/Y_xPr_1−xBa₂Cu₃O_y and YBa₂Cu₃Oy/R_1−xM_xMnO₃ superlattices in magnetic fields in which R=La or Nd, and M=Ca or Sr. The X-ray diffraction of samples shows superlattice structure. The resistive transition in a magnetic field shows thermal activated behavior. The flux pinning is reduced when the coupling strength between YBCO layers is decreased. The angular dependence of the critical current of YBa₂Cu₃O_y/PrBa₂Cu₃O_y superlattices reveals the dimensionality of superlattices. The magnetoresistance ratio (MR), |Δρ(H=7 T)−Δρ(H=0)|/Δρ(H=7 T), of YBa₂Cu₃O_y/R_1−xM_xMnO₃ superlattices is affected by the layer coupling of R_1−xM_xMnO₃ layers. The enhancement of the MR ratio in the tri-layer YBa₂Cu₃O_y/La_0.7M_0.3MnO₃/YBa₂Cu₃O_y film in the low temperature regime is significant and has a value of 33650% at T=75 K. We attribute this enhancement of the MR to the ordering of magnetic moment in ferromagnetic layers in magnetic fields. The results are discussed in terms of existing theories.     

57Fe Mössbauer spectroscopy and magnetization study of YFexAl12−x (4.4⩽x⩽5)

YFe_xAl_12−x in the composition range 4.4⩽x⩽5 was prepared by induction melting followed by annealing in vacuum at 1270 K. Magnetization data below 150 K show complex magnetic behaviour dependent on applied field, composition and temperature. The transition temperature T_c, corresponding to the main maximum of the magnetization vs. temperature curves and below which magnetic interactions are observed for a significant fraction of the Fe atoms in the Mössbauer spectra, decreases from 180 K for x=4 down to 100 K for 4.2⩽x⩽4.7 and rises again up to 160 K for x=5. The analysis of the spectra obtained at 5 K is consistent with full occupation of the 8f sites by Fe atoms and sharing of the 8j sites by Fe and Al as deduced from the Rietveld analysis of X-ray powder diffraction data. The Mössbauer spectra further show a dependence of magnetic hyperfine fields and isomer shifts on the crystallographic site and on the number of the Fe nearest neighbours similar to that observed in UFe_xAl_12−x (4⩽x⩽6) and RFe_xAl_12−x (R=Y, Lu, x=4, 4.2). The magnetic properties of the UFe_xAl_12−x and YFe_xAl_12−x series are compared and the magnetic interactions between the different Fe sublattices are discussed.     

Crystallography,magnetic properties and magnetocaloric effect in Gd4(BixSb1−x)3 alloys

A study of magnetic and thermal properties has been carried out on the alloys from the Gd₄(Bi_xSb_1−x)₃ series with x=0, 0.25, 0.5, 0.75, and 1. All of the alloys are ferromagnetic below their respective Curie temperatures which vary from 266 K for x=0 to 332 K for x=1.0. The magnetocaloric effect calculated from the temperature and magnetic field dependencies of the magnetization and heat capacity is moderate when compared to that of other materials, which order in the same temperature range. Both the magnetic ordering and the magnetocaloric effect peak temperatures increase nearly linearly with the increasing Bi content. Experimental magnetocaloric effect data obtained from two different measurement techniques are in excellent agreement.     

Structure and magnetic properties of the intermetallic La2Co17−xMox (x=0.5, 1, 1.5, 2) and La2Co16−yFeyMo (y=0, 1, 2, 3, 4, 6) compounds

The effect of Mo and Fe atoms on the crystal structure and magnetic properties of the intermetallic La₂Co_17−xMo_x (x=0.5, 1, 1.5, 2), and La₂Co_16−yFe_yMo (y=0, 1, 2, 3, 4, 6) compounds have been studied by X-ray diffractometry, magnetic measurements and Mössbauer spectroscopy. All samples belong to the rhombohedral Th₂Zn₁₇-type structure and their lattice parameters a and c increase both with Mo and Fe content. From the La–Co–Mo samples only the one with x=0.5 presents planar anisotropy, whereas from the La–Co–Fe–Mo samples only the y=1 has uniaxial anisotropy. The magnetization M_S and the Curie temperature T_C decrease upon Mo substitution, whereas the anisotropy field H_A does not change significantly. In the Fe-substituted compounds M_S increases, but the Curie temperature increases slightly for 0⩽y⩽4 but decreases in y=6. The low temperature M–T curve shows that the samples La₂Co_16.5Mo_0.5, and La₂Co₁₀Fe₆Mo present a spin reorientation transitions at 70 and 260 K, respectively. Mössbauer samples were obtained for all Fe-containing samples in the temperature range 20–300 K. Above 260 K a jump in the values of the hyperfine fields and quadrupole splitting parameters is observed which can be associated to the spin reorientation.     

Synthesis and characterization of layered Li1−x(Ni0.5Co0.5)1−yFeyO2(0 ≤ (1 − x) ≤ 1 and 0 ≤ y ≤ 0.2) cathodes

Layered Li(Ni_0.5Co_0.5)_1−yFe_yO₂ cathodes with 0 ≤ y ≤ 0.2 have been synthesized by firing the coprecipitated hydroxides of the transition metals and lithium hydroxide at 700 °C and characterized as cathode materials for lithium ion batteries to various cutoff charge voltages (up to 4.5 V). While the y = 0.05 sample shows an improvement in capacity, cyclability, and rate capability, those with y = 0.1 and 0.2 exhibit a decline in electrochemical performance compared to the y = 0 sample. Structural characterization of the chemically delithiated Li_1−x(Ni_0.5Co_0.5)_1−yFe_yO₂ samples indicates that the initial O3 structure is maintained down to a lithium content (1 − x) ≈ 0.3. For (1 − x) < 0.3, while a P3 type phase is formed for the y = 0 sample, an O1 type phase is formed for the y = 0.05, 0.1 and 0.2 samples. Monitoring the average oxidation state of the transition metal ions with lithium contents (1 − x) reveals that the system is chemically more stable down to a lower lithium content (1 − x) ≈ 0.3 compared to the Li_1−xCoO₂ system. The improved structural and chemical stabilities appear to lead to better cyclability to higher cutoff charge voltages compared to that found before with the LiCoO₂ system.     

A co-doping approach towards enhanced ionic conductivity in fluorite-based electrolytes

A co-dopant strategy is used to investigate the effect that the elastic strain in the lattice has on the grain ionic conductivity of doped ceria electrolytes. Based on critical dopant ionic radius (r_c), different compositions in the Lu_xNd_yCe_1−x−yO_2−δ (x + y = 0.05, 0.10, 0.15, and 0.20) system are studied. Dopants are added such that the weighted average dopant ionic radius matches r_c for all the compositions. Dense ceramic discs are prepared using conventional solid oxide route and sintering methods. Precise lattice parameter measurements are used to calculate the lattice strain. The ionic conductivity of the samples is measured in the temperature range of 250 °C to 700 °C using two-probe electrochemical impedance spectroscopy technique. The elastic strain present in Lu_xNd_yCe_1−x−yO_2−δ system is found to be negligible when compared to Lu_xCe_1−xO_2−δ (negative) and Nd_xCe_1−xO_2−δ (positive) systems. Grain ionic conductivity of Lu_xNd_yCe_1−x−yO_2−δ (where x + y = 0.05) at 500 °C is observed to be 1.9 × 10^− 3 S/cm which is twice as high as that of Lu_0.05Ce_0.95O_2−δ. These results extend the validity of the r_c concept as a strategy for co-doping ceria electrolytes and open new designing avenues for solid oxide electrolytes with enhanced ionic conductivity.     

Structure and magnetic properties of co-sputtered Co–C thin films

We studied the structure and magnetic properties of co-sputtered Co_1−xC_x thin films using a transmission electron microscope (TEM) and a SQUID magnetometer. These properties were found to depend critically on deposition temperature, T_S, and composition, x. Generally, phase separation into metallic Co and graphite-like carbon phases proceeds with increasing T_S and decreasing x. Plan view and cross-sectional TEM images of the films prepared showed that Co grains about 10–20 nm in diameter and 30–50 nm in height are three-dimensionally separated by graphite-like carbon layers 1–2 nm thick. Optimum magnetic properties with saturation magnetization of 380 emu/cc and coercivity of 400 Oe were obtained for a film with x=0.5 and T_S=350°C.     

Dielectric and piezoelectric properties of (Bi1−x−yNdxNa1−y)0.5BayTiO3 lead-free ceramics

New lead-free (Bi_1−x−yNd_xNa_1−y)_0.5Ba_yTiO₃ ceramics were prepared by a conventional ceramic technique and their dielectric and piezoelectric properties were studied. X-ray diffraction studies reveal that Nd³⁺ and Ba²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) of rhombohedral and tetragonal phases is formed at 0.04 < y < 0.10. The partial substitutions of Nd³⁺ and Ba²⁺ decrease effectively the coercive field E_c and increase significantly the remanent polarization P_r. Because of lower E_c, larger P_r and the formation of the MPB, the piezoelectric properties of the ceramics are significantly enhanced at x/y = 0.02/0.06: d₃₃ = 150 pC/N and k_p = 30.5%. The ceramics exhibit relaxor characteristic, which is probably resulted from the cation disordering in the 12-fold coordination sites. The depolarization temperature T_d shows a strong compositional dependence and reaches a minimum value at the MPB. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both the polar and non-polar regions near the depolarization temperature T_d, which cause the polarization hysteresis loop become deformed near/above T_d.     

Effect of Ni deficit on the electronic structure and magnetic properties of PrNi2−xSb2

The influence of a Ni deficit in the nickel sublattice on the electronic and magnetic properties of PrNi_2−xSb₂ compound is investigated. The band structure is calculated using the LMTO method for x=0, 0.50, 1.0 and 1.5. At T=0 K the compound is antiferromagnetic with a magnetic moment on Pr close to 2.0 μ_B.     

High temperature properties of the n = 2 Ruddlesden–Popper phases (La,Sr)3(Fe,Ni)2O7−δ

The crystal chemistry and mixed conductor properties of the n = 2 member of the Ruddlesden–Popper (R–P) phases Sr_3−xLa_xFe_2−yNi_yO_7−δ with 0 ≤ x ≤ 0.3 and 0 ≤ y ≤ 1.0 have been studied at high temperature. High-temperature X-ray diffraction and thermogravimetric measurements of the equilibrium pO₂ (10^− 5 ≤ pO₂ ≤ 1 atm) in the temperature range 400 ≤ T ≤ 1000 °C indicate that the Sr₃FeNiO_7−δ phase is able to accommodate a large oxygen non-stoichiometry (δ ∼ 1.5) without structural transformations. The electrical conductivity and oxygen permeability increase with the substitution of Ni for Fe in the range 550 ≤ T ≤ 1000 °C. The electrical transport of the Sr₃FeNiO_7−δ phase is thermally activated and the activation energy decreases with the substitution of Ni for Fe for a given oxygen content. The increase in the oxygen permeation flux with increasing Ni content is due to an increasing oxygen non-stoichiometry and a lower activation energy for permeation.     

Magnetic properties of RNi1−xIn1+x (R=Gd–Er) compounds

AC and DC bulk magnetic measurements were performed for RNi_1−xIn_1+x (R=Gd–Er and x=0,0.1, 0.25) compounds. These compounds crystallize in the hexagonal ZrNiAl-type structure. The lattice parameters a and c for the RNiIn series decrease linearly with increasing number of 4f electrons. For nonstoichiometric RNi_1−xIn_1+x additional indium atoms occupy the 2(c) crystallographic site and the a parameter increases while the c parameter decreases with increasing indium content. The stoichiometric samples show ferromagnetic behavior with the critical temperature changing from 96 K for R=Gd to 9 K for R=Er. In the nonstoichiometric RNi_1−xIn_1+x compounds increase in the indium content leads to decrease in the ferromagnetic critical temperatures and to a change of the antiferromagnetic ordering for x=0.25 in the case of R=Dy, Ho and Er.     

Oxygen isotope effect in disordered underdoped and overdoped La2−xSrxCu1−yZnyO4 superconductors

The effect of oxygen isotopic substitution on the superconducting transition temperature has been studied for heavily underdoped and overdoped La_2?xSr_xCu_1?yZn_yO₄ compounds with different Zn contents in the CuO₂ plane. The effect of Zn on the isotope coefficient, α, was significantly more pronounced in the case of the underdoped (x = 0.09) compounds compared to the overdoped (x = 0.22) ones. The variation of α with disorder content can be described quite well within a model based solely on Cooper pair-breaking in the case of the underdoped compounds. This model fails to describe the behavior of α(y) for the overdoped samples, even though Zn still suppresses T_c very effectively at this hole (Sr) content, indicating that the Zn induced pair-breaking is still very much at play. We discuss the implications of these findings in details by considering the Zn induced magnetism, stripe correlations, and possible changes in the superconducting order parameter as hole content in the CuO₂ plane, p (≡x), is varied.     

Spin reorientation and magnetocrystalline anisotropy of (Nd1−xDyx) Fe14B

Spin reorientation and magnetocrytalline anisotropy of (Nd_1−xDy_x)₂Fe₁₄B (x=0.25, 0.5, 0.75) have been studied from mangetization curves of magnetically aligned powders. In (Nd_1−xDy_x)₂Fe₁₄B, the spin reorientation temperature (T_SR) decreases linearly on increasing Dy-substitution from 135 to 56 K with the ratio of ΔT_SR=−1.11 K/Dy at% in the composition range of 0⩽x⩽0.75. The spin reorientation angle at 4.2 K decreases on Dy-substitution from 30.4° at x=0 to 14.7° at x=0.75. From the investigation of the magnetocrystalline anisotropy at 4.2 K, the disappearance of the spin reorientation for compositions x≳0.85 is expected.     

Influence on magnetic properties of substitution of Co for Fe in TbFe11.3Nb0.7

The magnetic properties of Tb(Fe_1−xCo_x)_11.3Nb_0.7 compounds with x=0, 0.05, 0.1, 0.15, 0.2 and 0.3 have been investigated. All compounds studied crystallize in the ThMn₁₂-type of structure. Substitution of Co for Fe leads to a contraction of the unit-cell volume. The Curie temperature clearly increases with increasing Co content from 551 K for x=0 to 831 K for x=0.3. The magnetic moment of the transition-metal sublattice increases with increasing Co content from 22.2 μ_B/f.u. for x=0 to 23.1 μ_B/f.u. for x=0.3. As the temperature increases, a spin reorientation from easy-plane to easy-cone is found in all compounds investigated. The spin-reorientation temperatures T_sr have been derived from the temperature dependence of the magnetization in a low field and decrease monotonously with increasing Co content. The easy magnetization direction at room temperature has been determined by X-ray diffraction on magnetically-aligned powder samples. The influence of the substitution of Co for Fe on the magnetic anisotropy is discussed in terms of crystal-field theory.     

Impact of Pr on structural,superconducting and magnetic properties of Y1−xPrxBaSrCu3O7

We study the structural, superconducting and magnetic properties of the Y_1−xPr_xBaSrCu₃O₇ system with x=0.0, 0.20, 0.25, 0.30, 0.40, 0.50, 0.60, 0.75 and 1.0, from X-ray diffraction, AC and DC magnetic susceptibility measurements. X-ray diffraction results reveal that while Pr substitutes isostructurally until x=0.50 in Y_1−xPr_xBaSrCu₃O₇, for x=0.75 and 1.0 few small intensity un-reacted lines are observed in the spectrum. The orthorhombic distortion decreases with an increase in x. Both x=0.75 and 1.0 samples are tetragonal. The c lattice parameter of the substituted samples increases with x, indicating probable substitution of comparatively bigger ionic radii Pr^3+/4+ ion at Y³⁺ in Y_1−xPr_xBaSrCu₃O₇ system. The AC susceptibility results showed that the transition temperature T_c of the Y_1−xPr_xBaSrCu₃O₇ system decreases monotonically with an increase in x. Both x=0.75 and 1.0 samples do not show a superconducting transition down to 4.2 K. The critical concentration of Pr to completely suppress superconductivity in Y_1−xPr_xBaSrCu₃O₇ is higher (0.75) than that reported (0.55) for Y_1−xPr_xBa₂Cu₃O₇. DC magnetic susceptibility measurements done on PrBaSrCu₃O₇ and PrBa₂Cu₃O₇ samples at 0.5 T revealed that while the Pr ordering temperature seems to be 12 K for the former, the same is 17 K for the latter. These results indicate that the ordering temperature of Pr moments in RE_1−xPr_x : 123-type systems, which decides the Pr^4f hybridisation with the Cu–O conduction band has a direct connection to the suppression of superconductivity. The lower T_N of Pr explains the less destructive effect of the same on the superconductivity of the parent undoped system.     

Ferromagnetic semiconductor Ge1−x−ySnxMnyTe with phase transformation of ferroelectric type

It is expected that joint existence of ferromagnetic properties and ferroelectric structural phase transition in diluted magnetic semiconductors IV-VI leads to new possibilities of these materials. Temperature of ferroelectric transition for such crystals can be tuned by the change of Sn/Ge ratio. Magnetic susceptibility, Hall effect, resistivity and thermoelectric power of Ge_1−x−ySn_xMn_yTe single crystals grown by Bridgeman method (x=0.083-0.115; y=0.025-0.124) were investigated within 4.2-300 K. An existence of FM ordering at T_C∼50 K probably due to indirect exchange interaction between Mn ions via degenerated hole gas was revealed. A divergence of magnetic moment temperature dependences at T?T_C in field-cooled and zero-field-cooled regimes is obliged to magnetic clusters which are responsible for superparamagnetism at T>T_C≈T_f (freezing temperature) and become ferromagnetic at T_C arranging spin glass state at T<T_f≈T_C. Phase transition of ferroelectric type at T≈46 K was revealed. Anomalous Hall effect which allows to determine magnetic moment was observed.     

Thermoelectric properties of Cr1−xMoxSi2

The thermoelectric properties of Mo-substituted CrSi₂ were studied. Dense polycrystalline samples of Mo-substituted hexagonal C40 phase Cr_1−xMo_xSi₂ (x=0–0.30) were fabricated by arc melting followed by spark plasma sintering. Mo substitution substantially increases the carrier concentration. The lattice thermal conductivity of CrSi₂ at room temperature was reduced from 9.0 to 4.5 W m⁻¹ K⁻¹ by Mo substitution due to enhanced phonon–impurity scattering. The thermoelectric figure of merit, ZT, increases with increasing Mo content because of the reduced lattice thermal conductivity. The maximum ZT value obtained in the present study was 0.23 at 800 K, which was observed for the sample with x=0.30. This value is significantly greater than that of undoped CrSi₂ (ZT=0.13).     

Effect of doping on cohesive and thermophysical properties of MgB2

The effects of doping Al and Mn on the cohesive and thermophysical properties of MgB₂ have been investigated using a Rigid Ion Model (RIM). The interatomic potential of this model includes contributions from the long-range Coulomb attraction and the short-range overlap repulsion and the van der Waals attraction. This model has been applied to describe the temperature dependence of the specific heat of MgB₂, Mg_1−xAl_xB₂ (x = 0.1–0.9) and Mg_1−xMn_xB₂ (x = 0.01–0.04) in the temperature range 5 K ⩽ T ⩽ 1000 K. The calculated results on cohesive energy (ϕ), Bulk modulus (B_T), molecular force constant (f), Restrahalen frequency (ν₀), Debye temperature (Θ_D) and Gruneisen parameter (γ) are also reported for these materials. Our results on Bulk modulus, Restrahalen frequency and Debye temperature are closer to the available experimental data. The comparison between our calculated and available experimental results on the specific heat at constant volume for MgB₂ and Mg_1−xAl_xB₂ (x = 0.1–0.4), particularly, at lower temperatures has shown almost an excellent agreement. The trend of variation of the specific heat with temperature is more or less similar in pure and doped MgB₂.