Studies on electrical conduction behavior of La1‐3xCaxBaxSrxMnO3 synthesized by chemical route

In the manganite La_1‐xM_xMnO₃ (M = Ca, Ba, Sr) the doping concentration introduces a mixed valency (Mn³⁺, Mn⁴⁺) which governs the magnetic and electrical properties of the compound. The perovskite oxides La_1‐3xCa_xBa_xSr_xMnO₃ (x = 0.00, 0.05, 0.10) were prepared by chemical method. Single‐phase formation is confirmed by XRD studies. The electrical behavior of compositions with x = 0.00, 0.05 and 0.10 in the system La_1‐3xCa_xBa_xSr_xMnO₃ was studied in the temperature range 300‐420 K. It is observed that conductivity decreases with increasing temperature as well as dopants concentration. Metallic behavior of these compositions decreases with increasing dopants concentration (x). The microstructures of these samples have been characterized using scanning electron microscopy (SEM). (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural investigation of anion-deficient manganites La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3 − δ</Subscript>

The crystal structure of the anion-deficient manganites La_0.7Sr_0.3MnO_{3 ? δ} (δ = 0, 0.10, 0.15, 0.20) is investigated using high-resolution neutron diffraction. At room temperature, the crystal structure of the stoichiometric manganite La_0.7Sr_0.3MnO₃ and the anion-deficient manganite La_0.7Sr_0.3MnO_2.9 is satisfactorily described in rhombohedral space group R \(\bar 3\) c. The anion-deficient manganite La_0.7Sr_0.3MnO_2.85 is characterized by two perovskite phases with space groups R \(\bar 3\) c and 14/mcm. The crystal structure of the La_0.7Sr_0.3MnO_2.8 manganite corresponds to the structure of a perovskite phase with space group I4/mcm. It is established that the phase separation in the crystal structure of the La_0.7Sr_0.3MnO_{3 ? δ} manganites at a temperature of 293 K is associated with a nonuniform distribution of oxygen vacancies.     

Phase Formation,Crystal Structure and Electrical Properties of La212 Type Compound Substituted by Silver or Praseodymium

The La212 type compounds substituted by silver or praseodymium are prepared by solid state reaction method. It is found that compounds La_2‐xSr_xCa_0.5Pr_0.5Cu₂O₆, La_1.6Pr_0.4Ca_1‐xSr_xCu₂O₆ and La_2‐xPr_xCa_0.5Sr_0.5Cu₂O₆ can be formed for x=0.4‐1.1, 0‐0.5 and 0‐1.5, respectively. A new member of La212 type compounds, La_2‐xAg_xCaCu₂O₆ is also prepared. Their structures are verified by Rietveld structure refinement to belong to the structure type of La212 cuprate oxide with space group I4/mmm. Their electrical properties are investigated. La_1.65Ag_0.35CaCu₂O₆ displays metal‐like behavior and its resistivity decreases with the decrease of temperature from 300K to 4.2K.     

Influence of polymerizing agent on structure and spectroscopic properties of nano‐crystalline La0.8Sr0.2MnO3 powders

Strontium‐doped lanthanum manganite (La_1‐xSr_xMnO₃ or LSM) is the material most widely used on solid oxide fuel cells cathode. In this work, nano‐scale La_0.8Sr_0.2MnO₃ powders have been synthesized by polymeric precursor‐based methods using different polymerizing agents with the aim of evaluating the influence of this change in the final powder. The powders calcined at 700 °C for 2 h have been characterized by X‐ray diffraction (XRD), scanning electron microscopy (FE‐SEM) and Fourier transform infrared spectroscopy (FTIR) in order to investigate the quality of both synthesis routes. It is shown that the crystal structure and morphology of the particles are significantly dependent on the preparation conditions. Single phase and La_0.8Sr_0.2MnO₃ nano‐crystalline particles less than 30 nm were obtained using ethylene glycol as polymerizing agent. FTIR results have been indicated that only the powder obtained using gelatin presented small traces of hydroxyl groups on its surface. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Co nanoclusters as origin of ferromagnetism in sol‐gel synthesized Zn1‐xCoxO (x = 0.05, 0.10 and 0.15) samples

We report on the structural and magnetic properties of the polycrystalline samples of Zn_1‐xCo_xO (x = 0.05, 0.10 and 0.15) synthesized via sol‐gel route. The air sintered samples of all compositions exhibit paramagnetic behaviour at room temperature, on the other hand the same samples on annealing in Ar/H₂ atmosphere show room temperature ferromagnetism (RTFM) with enhanced magnetization. The value of magnetization increases with the Co concentration (x) in both the air sintered and Ar/H₂ annealed samples. The observed ferromagnetism in the Ar/H₂ annealed Zn_1‐xCo_xO (x = 0.05, 0.10 and 0.15) samples is attributed to the presence of Co nanoclusters as detected by XRD and FESEM‐EDAX. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spin relaxation in nanophased manganites

We present recent results obtained by DC and AC susceptibility, muon spin relaxation and neutron spin echo experiments in magnetically ordered La_0.7Pb_0.3MnO₃ and disordered La_0.7Pb_0.3Mn_0.8Fe_0.2O₃. These results aim to cover an extraordinary equivalent frequency range (from quasi-static experiments to almost the THz region) and give an overall picture of the processes within. The different relaxations observed are related either to the macroscopic long-ranged interactions among magnetic clusters (susceptibility techniques) and to short-ranged intracluster spin diffusion processes (muon and neutron techniques).     

Specific effects of nanometer scale size on magnetic ordering in La1−xCaxMnO3 (x = 0.1, 0.3 and 0.6) manganites

To check the impact of nano-size originated effects on the magnetic ordering in doped manganites, X-band electron magnetic resonance measurements were performed on nanometer sized and bulk samples of La_1?xCa_xMnO₃ (x = 0.1, 0.3 and 0.6). The model fittings of EPR signal parameters and complementary magnetic measurements indicate that bulk La_0.9Ca_0.1MnO₃ shows inhomogeneous confinement of charge carriers, leading to its mixed magnetic ordering. The carriers mobility within impurity-like band and ferromagnetic (FM)-like ground state are observed on nanocrystals of the same composition. The bulk La_0.7Ca_0.3MnO₃ demonstrates homogeneous FM order and band-like carrier mobility. The surface magnetic disorder in its nano-counterpart leads to appearance of two magnetic phases – a core phase (bulk-like in properties) and a surface phase with notably reduced temperature of magnetic ordering; neither double-exchange interaction nor carriers mobility exist between these phases. The size reduction induced effects in La_0.4Ca_0.6MnO₃ are: an increase of surface FM-like component and a decrease of the charge-ordering temperature. These findings allow us to conclude that the nano-scale effect on magnetic ordering in La_1?xCa_xMnO₃ system weakens progressively upon stabilization of the low temperature magnetic ground state with Ca-doping.     

On the synthesis and characterization of La doped MgB2 superconductor

We report the synthesis of La doped MgB₂ superconductors with nominal compositions Mg_1‐xLa_xB₂ (with x = 0.01, 0.03, 0.05, 0.07) by solid state reaction at ambient pressure. A special encapsulation technique has been used by us to prepare high quality superconducting MgB₂ samples. The bulk polycrystalline samples possess superconducting transition temperature T_c(R=0) ranging between 36‐39 K. It has been found that transport critical current density J_c of the samples change significantly with the doping level of La. A high transport (J_c) value ∼1.9 x 10³ A/cm² at 15 K has been achieved for Mg_0.97La_0.03B₂ sample. The XRD and TEM investigations indicate that the samples prepared by encapsulation method are devoid of MgO, which is generally found when synthesis of MgB₂ is done through sintering of Mg and B powders. The detailed microstructural investigations of Mg_0.97La_0.03B₂ specimens by transmission electron microscopy (TEM) reveal the presence of partial dislocation network, moiré fringes and superlattice structure in the as synthesized samples. The higher transport critical current density observed in Mg_0.97La_0.03B₂ superconductor has been attributed to the partial dislocations which are capable of providing pinning centres. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural,Morphological and Electrical Studies on Barium Strontium Titanate Thin Films Prepared by Sol‐Gel Technique

The crystal structure, surface morphology, compositional homogeneity and electrical properties of barium strontium titanate (BST) thin films are investigated. The films were deposited on bare silicon and platinum coated silicon substrates by spin coating process. The precursor solution with Ba/Sr ratio 70/30 was prepared by sol‐gel synthesis using metal alkoxides. The crystalline nature and morphology of the films are found to be strongly influenced by the heating cycle adopted to form the Ba_0.7Sr_0.3TiO₃ layer. The elemental composition analysis on the surface and in‐depth confirms the stoichiometry of the films. The dielectric constant at 100 kHz and dissipation factor at room temperature is found to be 120 and 0.0236 for the films with 400nm thickness annealed at 700°C for 2 hrs. The leakage current density of the film is found to be 4x10^‐8 A/cm² from I‐V measurements.     

Growth and optical characterization of cerium and lead‐doped Bi12TiO20 sillenite single crystals

Bi₁₂TiO₂₀ (BTO) single crystals doped with PbO and CeO₂ were grown by the Top Seeded Solution Growth (TSSG) technique from the liquid phase with nominal compositions of 10Bi₂O₃ : (1–x)TiO₂ : x PbO and 10Bi₂O₃ : (1–x)TiO₂ : xCeO₂ with x = 0.25 and 0.10. No growth‐related difficulties were encountered other than those typical of sillenite crystals. Samples with good optical quality were obtained and were characterized by optical absorption, dark current, spectral photocurrent dependence, optical activity and electro‐optic coefficient measurements. A comparison is made of the results of the optical measurements of doped and undoped BTO crystals. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Some structural considerations on the perovskite‐type A1‐ySryCo1‐xFexO3‐δ solid solution series

Solid solution series of La_1‐ySr_yCo_1‐xFe_xO_3‐δ were extensively studied in the past as cathode materials for solid oxide fuel cells. However, the crystal structure behavior of La_1‐ySr_yCo_1‐xFe_xO_3‐δ solid solution series when La‐ions are replaced with another rare‐earth ion or metallic alkaline earth metal is at present not fully understood. Here we report X‐ray powder diffraction measurements performed on samples of the Sm_0.8Sr_0.2Co_1‐xFe_xO_3‐δ solid solution series. This study demonstrates that the average A‐cation radius, as well as the Fe content (x), affects the structural modification of the A_1‐ySr_yCo_1‐xFe_xO_3+δ solid solution series significantly. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electron irradiation‐induced effects on optical spectra of (NH4)2ZnCl4: x Sr2+ single crystals

The effect of electron‐beam irradiation with different doses on optical constants of (NH₄)₂ZnCl₄: x Sr²⁺ crystals with x=0.000, 0.020, 0.039, 0.087 or 0.144 wt% has been studied. The optical transmission in the energy range 3.4‐6.4 eV was measured hence the absorption coefficient was computed as a frequency function. The absorption coefficient was also calculated as a function of electron‐beam dose. Irradiation with e‐beam did not affect the allowed indirect type of transition responsible for interband transitions of (NH₄)₂ZnCl₄: x Sr²⁺ crystals. Values of the optical energy gap E_g and optical moment E_p for electronic interband transition of unexposed and (NH₄)₂ZnCl₄: x Sr²⁺ crystals after e‐beam exposure were deduced. The area under the absorption band at 5.30 eV was used to evaluate the effect of e‐irradiation on optical parameters of samples with x=0.00, 0.020 or 0.039. A shift in the position and a nonmonotonic change in the intensity of this band with increasing e‐beam dose was observed. Changes in the E_g value were used to evaluate the effect of e‐beam exposure dose on (NH₄)₂ZnCl₄: x Sr²⁺ samples with x=0.087 or 0.144. The obtained results were compared with those obtained for the same crystals after irradiation with different γ‐doses.     

Ferromagnetic insulating and reentrant spin glass behavior in Mg doped La0.75Sr0.25MnO3 manganites

In this study, the effect of Mg substitution on structural, magnetic and electrical properties of La_0.75Sr_0.25Mn_1?xMg_xO₃ and La_0.75Sr_0.25?xMg_xMnO₃ (nominal compositions) samples are investigated by XRD, Ac susceptibility and electrical resistivity measurements. It is found that Mg does not replace La in the perovskite lattice. Also the results show that by increasing Mg doping levels, the paramagnetic–ferromagnetic and metal–insulator transition temperatures decrease. The reason for decreasing transition temperatures with increasing Mg concentration is, that the long-range FM order has been destroyed by the Mg, which is randomly occupying Mn site. This leads to the suppression of double-exchange interaction in the Mn³⁺–O–Mn⁴⁺ networks. Also the reentrant spin glass (RSG) state accompanied by FM transition, exists in high doped samples. The RSG state could be understood on the basis of double exchange ferromagnetic interaction in Mn³⁺–O–Mn⁴⁺ and super-exchange antiferromagnetic interaction in the Mn⁴⁺–O–Mn⁴⁺ networks.     

Influence of cellular substructure on the thermal conductivity of heterovalent solid solutions of fluorides

The thermal conductivity of single-crystal samples of Sr_0.88La_0.09Nd_0.03F_2.03 and Sr_0.80La_0.15Nd_0.05F_2.20 solid solutions, both with a cellular substructure and without it, have been investigated by the method of stationary longitudinal heat flow in the temperature range of 50–300 K. An anisotropy of thermal conductivity (related to the substructure) is established for a Sr_0.995Nd_0.005F_2.005 single crystal.     

Enhancement of ferroelectricity in the compositionally graded (Pb,Sr)TiO3 thin films derived by a sol–gel process

The compositionally graded Pb_1−xSr_xTiO₃ (PST) films with a fine compositional gradient from Pb_0.6Sr_0.4TiO₃ to Pb_0.3Sr_0.7TiO₃ were fabricated on LNO-buffered Pt/Ti/SiO₂/Si substrates by a sol–gel deposition method. The graded films crystallized into a pure perovskite structure and exhibited highly (1 0 0) preferred orientation after post-deposition annealing. Dielectric and ferroelectric properties were investigated as a function of temperature, frequency and direct current bias field. Dielectric constant peaks, common to a ferroelectric transition, were not observed in the temperature range of 25–250 °C within which the dielectric constant showed weak temperature dependence. This compositionally graded thin film can result in a dielectric constant more than double and a remanent polarization at least two and a half times larger than conventional PST thin films.     

Microstructural,thermal, and electrical properties of Bi1.7V0.3Sr2Ca2Cu3Ox glass‐ceramic superconductor

A glass‐ceramic Bi_1.7V_0.3Sr₂Ca₂Cu₃O_x superconductor was prepared by the melt‐quenching method. The compound was characterized by scanning electron microscopy, x‐ray diffraction, differential thermal analysis, current‐voltage characteristics, transport resistance measurements, and Hall effect measurements. Two main phases (BSCCO 2212 and 2223) were observed in the x‐ray data and the values of the lattice parameters quite agree with the known values for 2212 and 2223 phases. The glass transition temperature was found to be 426 °C while the activation energy for crystallization of glass has been found to be E_a = 370.5 kJ / mol. This result indicates that the substitution of vanadium increased the activation energy for the BSCCO system. An offset T_c of 80 K was measured and the onset T_c was 100 K. The Hall resistivity ρ_H was found to be almost field‐independent at the normal state. A negative Hall coefficient was observed and no sign reversal of ρ_H or R_H could be noticed. The mobility and carrier density at different temperatures in the range 140‐300 K under different applied magnetic fields up to 1.4 T were also measured and the results are discussed. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electronic structure and magnetooptical properties of an La<Subscript>0.7</Subscript>Ca<Subscript>0.25</Subscript>Ba<Subscript>0.05</Subscript>MnO<Subscript>3</Subscript> single crystal

The spectral and temperature characteristics of the magnetooptical Kerr effect and the optical properties of an La_0.7Ca_0.25Ba_0.05MnO₃ single crystal are studied. The data obtained are used to calculate the components of the permittivity tensor, whose behavior is interpreted within the framework of the known models of the electronic structure of manganites.     

Floating zone growth and compositional inhomogeneity study of La0.75Y0.05Sr0.2MnO3 single crystals

Single crystals of La_0.75Y_0.05Sr_0.2 MnO₃ have been grown by the floating zone technique. The yttrium distribution in the radial and axial directions in the crystals was studied for different growth rates. The sample grown at high rate showed inhomogeneity in the yttrium content in the growth direction, while the sample grown at relatively low rate was homogeneous in the growth direction, but demonstrated compositional separation between the Y-poor central part and Y-enriched peripheral part in the perpendicular plane. The compositional separation led to magnetic inhomogeneity.     

Paramagnetic behavior of Zn1−xMnxO at room temperature

Mn‐doped ZnO were synthesized by solid state reaction and sol‐gel method respectively. It was found that samples synthesized by solid state reaction containing Mn₂O₃ and MnO₂ are a mixture of ferromagnetic and paramagnetic phases. Contrary, samples without second phases were found to be paramagnetic at room temperature. According to previous report, interface effects between Zn‐rich Mn₂O₃ and MnO₂ interfaces may be the origin of the ferromagnetic behavior observed in our samples prepared by solid reaction, so the alloy of Zn_1−xMn_xO may be paramagnetic at room temperature. Prepared by sol‐gel technique, the samples without second phases in the XRD patterns are also room‐temperature paramagnetic. Therefore we believe that the magnetism of Zn_1−xMn_xO is paramagnetic at room temperature. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and Characterization of Ml2-Intercalated Bi-2212 Cuprates (M=Mn,Fe, Co,Cu, Zn)

Abstract

A series of new layered cuprates with the composition MI_2+xBi₂Sr₂CaCu₂O_8+y (x=0.6–0.9; M=Mn, Fe, Co, Cu, Zn) have been synthesized by the reaction of Bi₂Sr₂CaCu₂O₈ with each transition metal under an atmosphere of iodine at 400°C. The new cuprates, lamellar in shape, are crystallized in a tetragonal unit cell with the lattice parameters of a = 5.393–5.402 Å and c = 43.32–43.96 Å. A structure model for these cuprates are proposed in which the monoiodide anions are intercalated in the Bi₂O₂ layer to form a bilayer accompanying 3d metal cations. All of the intercalated cuprates are non-superconducting to be as high as 0.74–2.52 MΩ · cm in resistivity at room temperature.