Structural, magnetic and magnetotransport behavior of some Nd-based perovskite manganites

A systematic investigation of Neodymium based colossal magnetoresistive manganites with general formula Nd_0.67A_0.33MnO₃, (A=Ca, Sr, Pb and Ba) has been undertaken mainly to understand their structural, magnetic as well as electrical behavior. The materials were prepared by the sol-gel route sintering at 900 °C. After usual characterization of the materials structurally by XRD, their metal-insulator transition (T_P) as well as magnetic transition (T_C) temperatures were determined and the reasons for the occurrence of ΔT_T(T_C-T_P) values have been explained. X-ray data have been analyzed by using Rietveld analysis and the variations of various parameters are explained. It has been concluded that not only A-site cation radius, 〈r_A〉 but also the size variance factor (σ²) influence both the metal-insulator as well as ferro to para magnetic transition temperatures. A systematic study of electrical conductivity of all the four materials was undertaken as a function of magnetic field upto 7 T mainly to understand the conduction mechanism in the presence of magnetic field. On analyzing the electrical resistivity data, it has been concluded that the metallic (ferromagnetic) part of the resistivity (ρ) (below T_P) can be explained by electron-electron scattering processes (∼T²) and two magnon scattering processes (∼T^4.5), while in the high temperature (T>T_P) paramagnetic insulating regime, the adiabatic small polaron and variable range hopping models are found to fit well.     

Physical properties and anisotropies of the RNiGe3 series (R = Y, Ce-Nd, Sm, Gd-Lu)

We have studied RNiGe₃ (R=Y, Ce-Nd, Sm, Gd-Lu) single crystals by measuring crystal structure and stoichiometry, magnetic susceptibility, magnetization, electrical resistivity, magnetoresistance, and specific heat. Clear anisotropies as well as antiferromagnetic ordering in the RNiGe₃ series (R=Ce-Nd, Sm, Gd-Tm) have been observed above 1.8 K from the magnetic susceptibility. A metamagnetic transition in this family (except for R=Sm) was detected at 2 K for applied magnetic fields below 70 kOe. The electrical resistivity of this series follows metallic behavior in the high temperature region. Below the antiferromagnetic ordering temperature a significant anisotropy is exhibited in the resistivity and magnetoresistance for different current directions. The anisotropic magnetic, transport, and thermal properties of RNiGe₃ compounds are discussed in terms of Ni site occupancy as well as a combination of the effect of formation of a magnetic superzone gap and the crystalline electric field.     

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.     

Co-existence of giant magnetoresistance and large magnetocaloric effect near room temperature in nanocrystalline La0.7Te0.3MnO3

Sol-gel prepared nanocrystalline La_0.7Te_0.3MnO₃ has rhombohedral crystal structure (space group R3¯C) at room temperature and orders ferromagnetically at ∼280 K (T_C). A large magnetic entropy change of ∼12.5 J kg⁻¹ K⁻¹ is obtained near T_C for a field change of 50 kOe. This magnetocaloric effect could be explained in terms of Landau theory. The temperature dependence of electrical resistivity shows metal-insulator transition at T_C and a giant magnetoresistance of ∼52% in 50 kOe. The co-existence of giant magnetoresistance and large magnetocaloric effect near room temperature makes nanocrystalline La_0.7Te_0.3MnO₃ a promising material for magnetic refrigeration and spintronic device applications.     

Investigation of magnetocaloric effect in La0.45Pr0.25Ca0.3MnO3 by magnetic,differential scanning calorimetry and thermal analysis

We investigated magnetocaloric effect in La_0.45Pr_0.25Ca_0.3MnO₃ by direct methods (changes in temperature and latent heat) and indirect method (magnetization isotherms). This compound undergoes a first-order paramagnetic to ferromagnetic transition with T_C=200 K upon cooling. The paramagnetic phase becomes unstable and it transforms into a ferromagnetic phase under the application of magnetic field, which results in a field-induced metamagnetic transition (FIMMT). The FIMMT is accompanied by release of latent heat and temperature of the sample as evidenced from differential scanning calorimetry and thermal analysis experiments. A large magnetic entropy change of ΔS_m=−7.2 J kg⁻¹ K⁻¹ at T=212.5 K and refrigeration capacity of 228 J kg⁻¹ are found for a field change of ΔH=5 T. It is suggested that destruction of magnetic polarons and growth of ferromagnetic phase accompanied by a lattice volume change with increasing magnetic field is responsible for the large magnetocaloric effect in this compound.     

Dielectric and AC ionic conductivity investigations in K3H(SeO4)2 single crystal

Optical observation under the polarizing microscope and DSC measurements on K₃H(SeO₄)₂ single crystal have been carried out in the temperature range 25-200 °C. It reveals a high-temperature structural phase transition at around 110 °C. The crystal system transformed from monoclinic to trigonal. Electrical impedance measurements of K₃H(SeO₄)₂ were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The temperature dependence of electrical conductivity indicates that the sample crystal became a fast ionic conductor in the high-temperature phase. The frequency dependence of conductivity follows the Jonscher's universal dynamic law with the relation σ(ω)=σ(0)+Aωⁿ, where ω is the frequency of the AC field, and n is the exponent. The obtained n values decrease from 1.2 to 0.1 from the room temperature phase to fast ionic phase. The high ionic conductivity in the high-temperature phase is explained by the dynamical disordering of protons between the neighboring SeO₄ groups, which provide more vacant sites in the crystal.     

Measurement of surface resistivity/conductivity of metallic alloys in aqueous solutions by optical interferometry techniques

Optical interferometry techniques were used for the first time to measure the surface resistivity/conductivity of the pure aluminium (in seawater at room temperature), UNS No.304 stainless steel (in seawater at room temperature), and pure copper (in tap water at room temperature) without any physical contact. This was achieved by applying an electrical potential across the alloys and measuring the current density flow across the alloys, during the cyclic polarization test of the alloys in different solutions. In the mean time, optical interferometry techniques such as holographic interferometry were used in situ to measure the orthogonal surface displacement of the alloys, as a result of the applied electrical potential. In addition, a mathematical model was derived in order to correlate the ratio of the electrical potential to the current density flow (electrical potential/electronic current flow = resistance) and to the surface (orthogonal) displacement of the metallic samples. In other words, a proportionality constant (surface resistivity or conductivity = 1/surface resistivity) between the measured electrical resistance and the surface displacement (by the optical interferometry techniques) was obtained. Consequently the surface resistivity (ρ) and conductivity (σ) of the pure aluminium (in seawater at room temperature), UNS No.304 stainless steel (in seawater at room temperature), and pure copper (in tap water at room temperature) were obtained. Also, electrical resistivity values (ρ) from other source were used for comparison sake with the calculated values of this investigation. This study revealed that the measured value of the resistivity for the pure aluminium (7.7 × 10¹⁰ Ω cm in seawater at room temperature) is in good agreement with the one found in literature for the aluminium oxide, 85% Al₂O₃ (5 × 10¹⁰ Ω cm in air at temperature 30 °C). Unfortunately, there is no measured value for the resistivity of cupric oxide (CuO), cuprous oxide (Cu₂O), or even the oxide of the UNS No.304 stainless steel in literature comparing those values with the measured values in this study.     

Dielectric properties and relaxation behavior of [TMA]2Zn0.5Cu0.5Cl4 compound

The [TMA]₂Zn_0.5Cu_0.5Cl₄ hybrid material was prepared and its dielectric spectra were measured in the 10⁻¹ Hz-10⁶ Hz frequency range and 200-305 K temperature interval. The dielectric permittivity showed a ferroelectric-paraelectric phase transition at 293 K. Double relaxation peaks are observed in the imaginary part of the electrical modulus, suggesting the presence of grain and grain boundary in the sample. The frequency dependent conductivity was interpreted in term of Jonscher's law: σ(ω)=σ_dc+Aωⁿ. The temperature dependent of the dc conductivity (σ_dc) was well described by the Arrhenius equation: σ_dcT=σ_o×exp(−E_a/kT).     

Crystal structure,NMR study,dielectric relaxation and AC conductivity of a new compound [Cd3(SCN)2Br6(C2H9N2)2]n

The crystal structure, the ¹³C NMR spectroscopy and the complex impedance have been carried out on [Cd₃(SCN)₂Br₆(C₂H₉N₂)₂]_n. Crystal structure shows a 2D polymeric network built up of two crystallographically independent cadmium atoms with two different octahedral coordinations. This compound exhibits a phase transition at (T=355±2 K) which has been characterized by differential scanning calorimetry (DSC), X-rays powder diffraction, AC conductivity and dielectric measurements. Examination of ¹³C CP/MAS line shapes shows indirect spin–spin coupling (¹⁴N and ¹³C) with a dipolar coupling constant of 1339 Hz. The AC conductivity of this compound has been carried out in the temperature range 325–376 K and the frequency range from 10⁻² Hz to 10 MHz. The impedance data were well fitted to two equivalent electrical circuits. The results of the modulus study reveal the presence of two distinct relaxation processes. One, at low frequency side, is thermally activated due to the ionic conduction of the crystal and the other, at higher frequency side, gradually disappears when temperature reaches 355 K which is attributed to the localized dipoles in the crystal. Moreover, the temperature dependence of DC-conductivity in both phases follows the Arrhenius law and the frequency dependence of σ(ω,T) follows Jonscher's universal law. The near values of activation energies obtained from the conductivity data and impedance confirm that the transport is through the ion hopping mechanism.     

Materials and ion transport property studies on hot-press casted solid polymer electrolyte membranes: [(1 − x) PEO: x KIO3]

Materials and ion transport property characterization in Solid Polymer Electrolyte (SPE) membranes: (1 − x) PEO: x KIO₃, where x = 0, 10, 20, 30, 40, 50 wt.%, have been studied. SPE films have been prepared following two casting techniques: a novel hot-press (extrusion) and the traditional solution cast. Hot-press technique is a completely dry/solvent free/rapid/inexpensive procedure as compared to solution cast method and has recently been receiving wider acceptability to cast membranes of ion conducting polymeric electrolytes.‘Log σ − x’ study revealed σ-maxima at salt concentration x = 30 wt.% for SPE film prepared by both the methods. However, hot-pressed SPE film: 70 PEO: 30 KIO₃ exhibited relatively higher room temperature conductivity (σ ∼ 4.40 × 10^− 7 S cm^− 1) than that of the solution casted film. This has been referred to as Optimum Conducting Composition (OCC) SPE film. Materials characterization in OCC SPE film has been done by XRD, FTIR and DSC techniques. These studies confirmed the complexation of salt in the polymeric host. Some basic ionic parameters viz. conductivity (σ), ionic mobility (μ), mobile ion concentration (n), ionic transference number (t_ion) have been determined using different experimental procedures to understand the ion transport behaviour in OCC SPE material. The temperature dependent conductivity measurement has also been carried out and the activation energy (E_a) has been computed from the linear least square fitting of ‘log σ − 1 / T’ Arrhenius plot.     

Effect of deposition pressure on structural, optical and electrical properties of zinc selenide thin films

ZnSe thin films have been prepared by inert gas condensation method at different gas pressures. The influence of deposition pressure, on structural, optical and electrical properties of polycrystalline ZnSe films have been investigated using X-ray diffraction (XRD), optical transmission and conductivity measurements. The X-ray diffraction study reveals the sphalerite cubic structure of the ZnSe films oriented along the (1 1 1) direction. The structural parameters such as particle size [6.65-22.24 nm], strain [4.01-46.6×10⁻³ lin⁻² m⁻⁴] and dislocation density [4.762-18.57×10¹⁵ lin m⁻²] have been evaluated. Optical transmittance measurements indicate the existence of direct allowed optical transition with a corresponding energy gap in the range 2.60-3.00 eV. The dark conductivity (σ_d) and photoconductivity (σ_ph) measurements, in the temperature range 253-358 K, indicate that the conduction in these materials is through an activated process having two activation energies. σ_d and σ_ph values decrease with the decrease in the crystallite size. The values of carrier life time have been calculated and are found to decrease with the reduction in the particle size. The conduction mechanism in present samples has been explained, and the density of surface states [9.84-21.4×10¹³ cm⁻²] and impurity concentration [4.66-31.80×10¹⁹ cm⁻³] have also been calculated.     

Room temperature magnetic entropy change and magnetoresistance in La0.70(Ca0.30−xSrx)MnO3:Ag 10% (x=0.0−0.10)

The magnetic and magnetocaloric properties of polycrystalline La_0.70(Ca_0.30−xSr_x)MnO₃:Ag 10% manganite have been investigated. All compositions are crystallized in single phase orthorhombic Pbnm space group. Both, the insulator–metal transition temperature (T^IM) and Curie temperature (T_c) are observed at 298 K for x=0.10 composition. Though both T^IM and T_c are nearly unchanged with Ag addition, the MR is increased. The MR at 300 K is found to be as large as 31% with magnetic field change of 1 T, whereas it reaches up to 49% at magnetic field of 3 T for the La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample. The maximum entropy change (ΔS_Mmax) at near its T_c (300.5 K) is 7.6 J kg⁻¹ K⁻¹ upon the magnetic field change of 5 T. The La_0.70Ca_0.20Sr_0.10MnO₃:Ag_0.10 sample having good MR (31%^1 T, 49%^3 T) and reasonable change in magnetic entropy (7.6 J kg⁻¹.K⁻¹, 5 T) at 300 K can be a potential magnetic refrigerant material at ambient temperatures.     

Metal-insulator transition induced by the magnetic field in n-type GaSb

The metal-insulator (MI) transition induced by a magnetic field was evidenced for the first time in compensated n-type GaSb layers grown by molecular beam epitaxy. The free electron densities were in the low 10¹⁶ cm⁻³ range or even slightly lower, so that the zero-field 3D electron gas was degenerate and, at the B_MI magnetic field of the MI transition, it populates only the spin-split 0⁽⁺⁾ Landau level (extreme quantum limit). On the metallic side of the MI transition a T^1/3 dependence of the conductivity was assumed to fit the low-T data and to estimate the B_MI value, which resulted of 9.1 T in the purest sample. The MI transition manifests in a strong increase of the diagonal resistivity with the magnetic field, but not of the Hall coefficient, suggesting that the apparent electron density is practically constant, whereas the mobility varies strongly. The evidence of a maximum in the temperature dependence of the Hall coefficient has been explained through a two channels transport mechanism involving localized and extended states.     

Phase and electrical behaviour in the Bi14W1 − xLaxO24 − 3x/2 system

The compositional and thermal dependencies of phase and electrical behaviour of compositions in the system Bi₁₄W_1 − xLa_xO_{24 − 3x/2} (0.00 < x < 1.00) have been studied by X-ray powder diffraction, differential thermal analysis and a.c. impedance spectroscopy. The system exhibits polymorphism and phase separation, which shows both compositional and thermal dependence. Compositions with x = 0.25 and x = 0.50 exhibit a single phase tetragonal structure at room temperature. In contrast, the x = 0.75 composition at room temperature shows a mixture of a cubic phase and a secondary β-Bi₂O₃ related tetragonal phase. A full solid solution is observed at high temperatures, corresponding to the occurrence of a δ-Bi₂O₃ type phase. The appearance of the various phases correlates well with the observed electrical behaviour. The x = 0.75 composition exhibits exceptionally high conductivity at high temperatures (σ₈₀₀ = 1.34 S cm^− 1), but also shows significant phase separation at lower temperatures.     

In-situ control of different oxygen fugacity experimental study on the electrical conductivity of lherzolite at high temperature and high pressure

At pressure 1.0-4.0 GPa and temperature 1073-1423 K and under the control of oxygen fugacity (Mo+MoO₂, Fe+FeO and Ni+NiO), a YJ-3000t multi-anvil solid high-temperature and high-pressure apparatus and Solartron-1260 impedance/Gain-Phase analyzer were employed to analyze the electrical conductivity of lherzolite. The experimental results showed that: (1) within the range of the selected frequencies (10³-10⁶ Hz), either as viewed from the relationship between the real or imaginary part of complex impedance and the frequency, or from the relationship between modulus, phase angle and frequency, it can be seen clearly that the complex impedance has a strong dependence on frequency; (2) with the rise of temperature (T), the electrical conductivity (σ) increased, and Lg σ and 1/T follows the Arrhenius relationship; (3) with the rise of pressure, the electrical conductivity decreased, and activation enthalpy and temperature-independent pre-exponential factor decreased as well. And the activation energy and activation bulk volume of the main charge carrier in the lherzolite have been obtained for the first time, which are 1.68±0.02 eV and 0.04±0.01 cm³/mol, respectively; (4) under the given pressure and temperature, the electrical conductivity tends to increase with increasing oxygen fugacity, and under the given pressure, the activation enthalpy and pre-exponential factor tend to decrease with the rise of oxygen fugacity; (5) at 2.0 GPa and the control of the three solid buffers, Mo+MoO₂, Fe+FeO and Ni+NiO, the exponential factors of electrical conductivity variation range with oxygen fugacity are , and the theoretical model for the relationship between the electrical conductivity of lherzolite and the oxygen fugacity under high pressure has been established for the first time; (6) the electrical conduction mechanism of small polarons provides a reasonable explanation to the variation of conductivity of lherzolite with oxygen fugacity.     

Structural, magnetic and magnetotransport behavior of La0.7SrxCa0.3−xMnO3 compounds

A systematic investigation of the structural, magnetic and electrical properties of a series of nanocrystalline La_0.7Sr_xCa_0.3−xMnO₃ materials, prepared by high energy ball milling method and then annealed at 900 °C has been undertaken. The analysis of the XRD data using the Win-metric software shows an increase in the unit cell volume with increasing Sr ion concentration. The La_0.7Sr_xCa_0.3−xMnO₃ compounds undergo a structural orthorhombic-to-monoclinic transition at x=0.15. Electric and magnetic measurements show that both the Curie temperature and the insulator-to-metal transition temperature increase from 259 K and 253 K correspondingly for La_0.7Ca_0.3MnO₃ (x=0) to 353 K and 282 K, respectively, for La_0.7Sr_0.3MnO₃ (x=0.3). It is argued that the larger radius of Sr²⁺ ion than that of Ca²⁺ is the reason to strengthen the double-exchange interaction and to give rise to the observed increase of transition temperatures. Using the phenomenological equation for conductivity under a percolation approach, which depends on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the resistivity versus temperature data measured in the range of 50-320 K and found that the activation barrier decreased with the raising Sr²⁺ ion concentration.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Structural,optical and dielectric properties of Ni substituted NdFeO3

Present study reports the structural, optical and dielectric properties of Ni substituted NdFe_1−xNi_xO₃ (0 ≤ x ≤ 0.5) compounds prepared through the ceramic method. X-ray diffraction (XRD) confirmed an orthorhombic crystal structure of all the samples. Both unit cell volume and grain size were found to decrease with an increase in Ni concentration. Morphological study by Scanning electron microscope (SEM) shows less porosity with Ni substitution in present system. From UV–vis spectroscopy, the optical band gap was found to increase with Ni doping. This observed behavior was explained on the basis of reduction in crystallite size, unit cell volume and its impact on the crystal field potential of the system after Ni substitution. The dielectric properties (?′ and tanδ) as a function of frequency or temperature, and the ac electrical conductivity (σ_ac) as a function of frequency have been studied. Hopping of charge carriers between Fe²⁺ → Fe³⁺ ions and Ni²⁺ → Ni³⁺ ions are held responsible for both electrical and dielectric dispersion in the system. Wide optical band gap and a very high dielectric constant of these materials promote them to be a suitable candidate for memory based devices in electronic industry.     

Thermal, electrical, and electrochemical properties of Lanthanum-doped Ba0.5Sr0.5 Co0.8Fe0.2O3-δ

Crystal structure, thermogravimetry (TG), thermal expansion coefficient (TEC), electrical conductivity and AC impedance of (Ba_0.5Sr_0.5)_1-xLa_xCo_0.8Fe_0.2O_3-δ (BSLCF; 0.05?x?0.20) were studied in relation to their potential use as intermediate temperature solid oxide fuel cell (IT-SOFC) cathode. A single cubic pervoskite was observed by X-ray diffraction (XRD). The TEC of BSLCF was increasing slightly with the increasing content of La, and all the compounds showed abnormal expansion at high temperature. Proved by the TG result, it was associated with the loss of lattice oxygen. The electrical conductivity, which is the main defect of Ba_0.5Sr_0.5 Co_0.8Fe_0.2O_3-δ (BSCF), was improved by La doping, e.g., the compound of x=0.20 demonstrated a conductivity of σ=376 S cm⁻¹ at 392 °C. The increase of electrical conductivity resulted from the increased concentration of charge carrier induced by La doping. In addition, the AC impedance revealed the better electrochemical performance of BSLCF. For example, at 500 °C, the sample with composition x=0.15 yielded the resistance values of 2.12 Ω cm², which was only 46% of BSCF.     

The influence of Zn ions substitution on the transport properties of Mg-ferrite

The thermoelectric power and electrical conductivity measurements of Zn-substituted Mg-ferrites having the general formula Mg_1−xZn_xFe₂O₄ (where x=0, 0.2, 0.4 and 0.6) were carried out from room temperature to 773 K. The Seebeck coefficient is positive for all the compositions showing that these ferrites behave as p-type semiconductors and the majority charge carriers are holes. The temperature variation of the Seebeck coefficient is also discussed. The Fermi energy (E_F); the density of charge carriers (n) and the carriers mobility (μ) were determined for the studied system. The variation of log σ with reciprocal of temperature shows a discontinuity at Curie temperature. The DC electrical conductivity increases with increasing temperature ensuring the semiconducting nature of the samples. The Curie temperature determined from DC electrical conductivity was found in satisfactory agreement with that determined from initial magnetic permeability measurements. This transition temperature is found to decrease with increasing Zn concentration. The activation energy in the paramagnetic region is found to be lower than that in ferrimagnetic region. The variation of room temperature conductivity with composition indicates that conductivity increases with increasing Zn content. The dependence of the electrical conductivity of Mg-Zn ferrite on Zn content is explained on the basis of the cation distribution.