Ab initio study of disorder effects on the electronic and magnetic structure of Sr2FeMoO6

We have investigated the electronic structure of ordered and disordered Sr2FeMoO6 using ab initio bandstructure methods. The effect of disorder was simulated within supercell calculations to realize several configurations with mis-site disorders. It is found that such disorder effects destroy the half-metallic ferromagnetic state of the ordered compound. It also leads to a substantial reduction of the magnetic moments at the Fe sites in the disordered configurations. Most interestingly, it is found for the disordered configurations that the magnetic coupling within the Fe sublattice as well as that within the Mo sublattice always remain ferromagnetic, while the two sublattices couple antiferromagnetically, in close analogy to the magnetic structure of the ordered compound, but,in contrast to recent suggestions.

Reversible and irreversible switching processes in pure and lanthanum modified lead zirconate thin films

The mechanism of field induced phase switching in antiferroelectric lead zirconate and La-modified lead zirconate thin films has been analysed in terms of reversible and irreversible switching process under weak fields as a function of donor concentration. Extension of Rayleigh law of ferromagnetic materials to the present antiferroelectric and modified antiferroelectric compositions have clearly showed that origin of small signal dielectric permittivity is due to reversible domain wall motion. Rayleigh's constant, a measure of irreversible switching process, exhibited a slight increase with lower La3+ concentrations and followed by a gradual fall for higher concentration. This clearly illustrates that donor addition to antiferroelectric thin films controls the domain switching even under weak fields. (C) 2002 Elsevier Science B.V. All rights reserved.

System Dy-Fe-O: thermodynamic properties of ternary oxides using Calvet calorimetry and solid-state electrochemical cell

The enthalpy increments and the standard molar Gibbs energies of formation-of DyFeO3(s) and Dy3Fe5O12(s) have been measured using a Calvet micro-calorimeter and a solid oxide galvanic cell, respectively. A co-operative phase transition, related to anti-ferromagnetic to paramagnetic transformation, is apparent. from the heat capacity data for DyFeO3 at similar to 648 K. A similar type of phase transition has been observed for Dy3Fe5O12 at similar to 560 K which is related to ferrimagnetic to paramagnetic transformation. Enthalpy increment data for DyFeO3(s) and Dy3Fe5O12(s), except in the vicinity of the second-order transition, can be represented by the following polynomial expressions:{H(0)m(T) - H(0)m(298.15 K)) (Jmol(-1)) (+/-1.1%) = -52754 + 142.9 x (T (K)) + 2.48 x 10(-3) x (T (K))(2) + 2.951 x 10(6) x (T (K))(-1); (298.15 less than or equal to T (K) less than or equal to 1000) for DyFeO3(s), and {H(0)m(T) - H(0)m(298.15 K)} (Jmol(-1)) (+/-1.2%) = -191048 + 545.0 x (T - (K)) + 2.0 x 10(-5) x (T (K))(2) + 8.513 x 10(6) x (T (K))(-1); (208.15 less than or equal to T (K) less than or equal to 1000)for Dy3Fe5O12(s). The reversible emfs of the solid-state electrochemical cells: (-)Pt/{DyFeO3(s) + Dy2O3(s) + Fe(s)}/YDT/CSZ//{Fe(s) + Fe0.95O(s)}/Pt(+) and (-)Pt/{Fe(s) + Fe0.95O(s)}//CSZ//{DyFeO3(s) + Dy3Fe5O12(s) + Fe3O4(s)}/Pt(+), were measured in the temperature range from 1021 to 1250 K and 1035 to 1250 K, respectively. The standard Gibbs energies of formation of solid DyFeO3 and Dy3Fe5O12 calculated by the least squares regression analysis of the data obtained in the present study, and data for Fe0.95O and Dy2O3 from the literature, are given by Delta(f)G(0)m(DyFeO3,s)(kJmol(-1))(+/-3.2)= -1339.9 + 0.2473 x (T(K)); (1021 less than or equal to T (K) less than or equal to 1548)and D(f)G(0)m(Dy3Fe5O12,s) (kJmol(-1)) (+/-3.5) = -4850.4 + 0.9846 x (T (K)); (1035 less than or equal to T (K) less than or equal to 1250) The uncertainty estimates for Delta(f)G(0)m include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagram and chemical potential diagrams for the system Dy-Fe-O were developed at 1250 K. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

A new class of magnetic materials: Sr2FeMoO6 and related compounds

Ordered double perovskite oxides of the general formula A2BB′O6 have been known for several decades to have interesting electronic and magnetic properties. However, a recent report of a spectacular negative magnetoresistance effect in a specific member of this family, namely Sr2FeMoO6, has brought this class of compounds under intense scrutiny. It is now believed that the origin of the magnetism in this class of compounds is based on a novel kinetically-driven mechanism. This new mechanism is also likely to be responsible for the unusually high temperature ferromagnetism in several other systems, such as dilute magnetic semiconductors, as well as in various half-metallic ferromagnetic systems, such as Heussler alloys.

Engineered Biferroic 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3/La0.6Sr0.4MnO3 Epitaxial Superlattices

Symmetric and asymmetric superlattices (SLs) composed of ferromagnetic La0.6Sr0.4MnO3 (LSMO) and ferroelectric 0.7Pb(Mg1/3Nb2/3)O3 – 0.3PbTiO3 (PMN-PT) with different periodicities have been fabricated on LaNiO3 (LNO) coated LaAlO3 (100) (LAO) substrates by pulsed laser ablation deposition. Structural, ferromagnetic and ferroelectric properties have been studied for all the SLs. All the heterostructures exhibited good ferromagnetic response over a wide range of temperatures (10K – 300K), whereas only the asymmetric SLs exhibited reasonably good ferroelectric behaviour. Ferromagnetic and ferroelectric hysteresis loops observed in the asymmetric SLs confirmed their biferroic nature. Studies were conducted towards understanding the influence of LSMO layers on the electrical responses of the heterostructures. Absence of ferroelectricity in the symmetric SL structures has been attributed to their high leakage characteristics. Strong influence of an applied magnetic field of 1.2T was observed on the ferroelectric properties of the asymmetric SLs. The effect of magnetic field on the ferroelectric properties of the SLs indicated possibility of strong interfacial effect.

Novel Mn-doped chalcopyrites

Heavily Mn-doped II-VI-V-2 semiconductors, such as CdGeP2 and ZnGeP2 have been prepared by depositing Mn on single crystalline substrate at nearly 400 T in an ultra high vacuum chamber. Well-defined ferromagnetic hysteresis with a saturation behavior appears in the magnetization curve up to above room temperature. The chemical states of the ZDGeP(2):Mn interface has been clarified by a careful in situ photoemission spectroscopy. The as-prepared surface consists of Ge-rich, metallic Mn compound. In and below the sub-surface region, dilute divalent Mn species as precursors of the DMS phase exist. No MnP phase was observed at any stage of the depth profile. Theoretical band-calculation suggests that the system with vacancies (Cd, V-c, Mn)GeP2 or a non-stoichiometric (Cd, Ge, Mn)GeP2 are ferromagnetic and energetically stable although ferromagnetism is not stable in a stoichiometric compound (Cd, Mn)GeP2. (C) 2003 Elsevier Ltd. All rights reserved.

Dicopper(II) complexes showing DNA hydrolase activity and monomeric adduct formation with bis(4-nitrophenyl)phosphate

Ferromagnetic dicopper(II) complexes [Cu(2)(mu-O(2)CCH(3))(mu-OH)(L)(2)(mu-L(1))](PF(6))(2), where L = 1,10-phenanthroline (phen), L(1) = H(2)O in 1 and L = dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), L(1) = CH(3)CN in 2, are prepared and structurally characterized. Crystals of 1 and 2 belong to the monoclinic space group of P2(1)/n and P2(1)/m, respectively. The copper(II) centers display distorted square-pyramidal geometry having a phenanthroline base and two oxygen atoms of the bridging hydroxo and acetate group in the basal plane. The fifth coordination site has weak axially bound bridging solvent molecule H(2)O in 1 and CH(3)CN in 2. The Cu center dot center dot center dot Cu distances are 3.034 and 3.046 angstrom in 1 and 2, respectively. The complexes show efficient hydrolytic cleavage of supercoiled pUC19 DNA as evidenced from the mechanistic studies that include T4 DNA ligase experiments. The binuclear complexes form monomeric copper(II) adducts [Cu(L)(2)(BNPP)](PF(6)) (L = phen, 3; dpq, 4) with bis(4-nitrophenyl)phosphate (BNPP) as a model phosphodiester. The crystal structures of 3 and 4 reveal distorted trigonal bipyramidal geometry in which BNPP binds through the oxygen atom of the phosphate. The kinetic data of the DNA cleavage reactions of the binuclear complexes under pseudo- and true-Michaelis-Menten conditions indicate remarkable enhancement in the DNA hydrolysis rate in comparison to the control data. (C) 2011 Elsevier B.V. All rights reserved.

Confinement-deconfinement transition and spin correlations in a generalized Kitaev model

We present a spin model, namely, the Kitaev model augmented by a loop term and perturbed by an Ising Hamiltonian, and show that it exhibits both confinement-deconfinement transitions from spin liquid to antiferromagnetic/spin-chain/ferromagnetic phases and topological quantum phase transitions between gapped and gapless spin-liquid phases. We develop a fermionic resonating-valence-bonds (RVB) mean-field theory to chart out the phase diagram of the model and estimate the stability of its spin-liquid phases, which might be relevant for attempts to realize the model in optical lattices and other spin systems. We present an analytical mean-field theory to study the confinement-deconfinement transition for large coefficient of the loop term and show that this transition is first order within such mean-field analysis in this limit. We also conjecture that in some other regimes, the confinement-deconfinement transitions in the model, predicted to be first order within the mean-field theory, may become second order via a defect condensation mechanism. Finally, we present a general classification of the perturbations to the Kitaev model on the basis of their effect on it's spin correlation functions and derive a necessary and sufficient condition, within the regime of validity of perturbation theory, for the spin correlators to exhibit a long-ranged power-law behavior in the presence of such perturbations. Our results reproduce those of Tikhonov et al. [Phys. Rev. Lett. 106, 067203 (2011)] as a special case.

Complete 'melting' of charge order in hydrothermally grown Pr0.57Ca0.41Ba0.02MnO3 nanowires

Nanowires of Pr0.57Ca0.41Ba0.02MnO3 (PCBM) (diameter similar to 80-90 nm and length similar to 3.5 mu m) were synthesized by a low reaction temperature hydrothermal method. Single-phase nature of the sample was confirmed by XRD experiments. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the morphology and microstructures of the nanowires. While the bulk PCBM is known to exhibit charge order (CO) below 230 K along with a ferromagnetic transition at 110 K, SQUID measurements on the nanowires of PCBM show that the charge order is completely absent and a ferromagnetic transition occurs at 115 K. However, the magnetization in the nanowires is observed to be less compared to that in the bulk. This observation of the complete 'melting' of the charge order in the PCBM nanowires is particularly significant in view of the observation of only a weakening of the CO in the nanowires of Pr0.5Ca0.5MnO3. Electron paramagnetic resonance experiments were also carried out on the PCBM nanowires using an X-band EPR spectrometer. Characteristic differences were observed in the line width of nanowires when compared with that of the bulk.

Transport properties and colossal magnetoresistance in epitaxial La0.67Cd0.33MnO3 thin film

An optimal composition of La0.67Cd0.33MnO3 was synthesized by ceramic route. The compound crystallized in a rhombohedral structure with lattice parameters a = 5.473(4) Å and α = 60°37′. Resistivity measurement showed an insulator-to-metal transition coupled with a ferromagnetic transition of around 255 K. Epitaxial thin films were fabricated on the LaAlO3 (100) substrate by a pulsed laser deposition technique. The psuedocubic lattice parameter a of the film is 3.873(4) Å. The insulator-to-metal transition of the film was observed at 250 K which is comparable with the bulk value. The film was ferromagnetic below this temperature. Magnetoresistance defined as ΔR/R0 = (RH−R0)/R0 was over −86% near the insulator-to-metal transition temperature of 240 K at 6 T magnetic field and over-30% at relatively low fields of 1 T. No magnetoresistance was observed at low temperatures in the film unlike in the polycrystalline sample, where about a 40% decrease in resistance was observed on applying 6 T magnetic field due to the spin dependent scattering at the grain boundaries.

Effect of particle size on the giant magnetoresistance of La0.7Ca0.3MnO3

Effect of particle size on the electron transport and magnetic properties of La0.7Ca0.3MnO3 has been investigated. While the ferromagnetic Tc, low field magnetic susceptibility, and insulator‐metal transition are markedly affected by the particle size, the maximum magnetoresistance exhibited by the samples near Tc is not sensitive to the particle size. However, the magnetoresistance at 4.2 K increases with decrease in particle size, suggesting a substantial contribution by the grain boundaries. Preliminary measurements on La0.7Sr0.3MnO3 samples of different particle sizes also corroborate the above conclusions.

Transport and magnetic properties of Nd1-xPbxMnO3 single crystals

Transport and magnetic properties of flux-grown Nd1−xPbxMnO3 single crystals (x=0.15–0.5) are studied in the temperature range 300–77 K and 280–2 K, respectively. Magnetization measurements with a superconducting quantum interference device confirm a paramagnetic to ferromagnetic transition around 110, 121, 150, 160, and 178 K for x=0.15, 0.2, 0.3, 0.4, and 0.5, respectively. Four probe resistivity measurements at low temperatures show a monotonic increase for x=0.15 which represents a ferromagnetic insulating (FMI) phase. For Nd0.8Pb0.2MnO3 there is a slope change present in the resistivity profile at 127 K where metal to insulator transition (MI) sets in. For x=0.3 this MI transition is more prominent. However, both these samples have FMI phase at low temperature. When the concentration of lead increases (x>0.3) the sample displays a clear insulator to metal transition with a low temperature ferromagnetic metallic phase. On the basis of these measurements we have predicted the phase diagram of Nd1−xPbxMnO3. Magnetization measurements by a vibration sample magnetometer point out the appreciable differences between zero field cooled and field cooled profiles below the ferromagnetic to paramagnetic transition temperature for all x. These are indicative of magnetic frustration.

Evidence for decoupled two-dimensional vortex behavior of YBa2Cu3O7-δ in La0.7Sr0.3MnO3/YBa2Cu3O7-δ/La0.7Sr0.3MnO3 trilayer

We investigate the vortex behavior of YBa2Cu3O7−δ thin films sandwiched between two ferromagnetic layers (La0.7Sr0.3MnO3/YBa2Cu3O7−δ/La0.7Sr0.3MnO3). The magnetization study on La0.7Sr0.3MnO3/YBa2Cu3O7−δ/La0.7Sr0.3MnO3 trilayers conspicuously shows the presence of both ferromagnetic and diamagnetic phases. The magnetotransport study on the trilayers reveals a significant reduction in the activation energy (U) for the vortex motion in YBa2Cu3O7−δ. Besides, the “U” exhibits a logarithmic dependence on the applied magnetic field which directly indicates the existence of decoupled two-dimensional (2D) pancake vortices present in the CuO2 layers. The evidence of 2D decoupled vortex behavior in La0.7Sr0.3MnO3/YBa2Cu3O7−δ/La0.7Sr0.3MnO3 is believed to arise from (a) the weakening of superconducting coherence length along the c-axis and (b) enhanced intraplane vortex–vortex interaction due to the presence of ferromagnetic layers.

Realization of biferroic properties in La0.6Sr0.4MnO3/0.7Pb(Mg1/3Nb2/3)O3–0.3(PbTiO3) epitaxial superlattices

A set of symmetric and asymmetric superlattices with ferromagnetic La0.6Sr0.4MnO3 (LSMO) and ferroelectric 0.7Pb(Mg1/3Nb2/3)O3–0.3(PbTiO3) as the constituting layers was fabricated on LaNiO3 coated (100) oriented LaAlO3 substrates using pulsed laser ablation. The crystallinity, and magnetic and ferroelectric properties were studied for all the superlattices. All the superlattice structures exhibited a ferromagnetic behavior over a wide range of temperatures between 10 and 300 K, whereas only the asymmetric superlattices exhibited a reasonably good ferroelectric behavior. Strong influence of an applied magnetic field was observed on the ferroelectric properties of the asymmetric superlattices. Studies were conducted toward understanding the influence of conducting LSMO layers on the electrical responses of the heterostructures. The absence of ferroelectricity in the symmetric superlattice structures has been attributed to their high leakage characteristics. The effect of an applied magnetic field on the ferroelectric properties of the asymmetric superlattices indicated strong influence of the interfaces on the properties. The dominance of the interface on the dielectric response was confirmed by the observed Maxwell-Wagner-type dielectric relaxation in these heterostructures.

Interface dominated biferroic La0.6Sr0.4MnO3/0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 epitaxial superlattices

Superlattices composed of ferromagnetic La0.6Sr0.4MnO3 and ferroelectric 0.7Pb(Mg1/3Nb2/3)O3–0.3(PbTiO3) layers were fabricated on (100) LaAlO3 substrates by pulsed laser deposition technique. The ferromagnetic and frequency independent ferroelectric hysteresis characteristics established the biferroic nature of the superlattices. Influence of magnetic field was observed in tuning the P-E characteristics of the superlattices. A similar effect was observed on application of a high dc electric field to the samples. The nature of the observed ferroelectric properties and their modulation by applied magnetic and electric fields were thus discussed in connection to the ferroelectric/ferromagnetic interfaces.