Investigating thermal stability of structural defects and its effect on d(0) ferromagnetism in undoped SnO2

The effect of annealing on structural defects and d(0) ferromagnetism in SnO2 nanoparticles prepared by solution combustion method is investigated. The as-synthesized SnO2 nanoparticles were annealed at 400-800 degrees C for 2 h, in ambient conditions. The crystallinity, size, and morphology of the samples were studied using x-ray diffraction and transmission electron microscopy studies. The annealing results in grain growth due to coarsening as well as reduction in oxygen vacancies as confirmed by Raman spectroscopy, photoluminescence spectroscopy, and x-ray photoelectron spectroscopy. All the as synthesized and annealed samples exhibit room temperature ferromagnetism (RTFM) with distinct hysteresis loops and the saturation magnetization as high as similar to 0.02 emu/g in as-synthesized samples. However, the saturation magnetization is drastically reduced with increasing annealing temperature. Further the presence of singly charged oxygen vacancies (V-o(-) signal at g-value 1.99) is confirmed by electron paramagnetic resonance studies, which also diminish with increasing annealing temperature. The observed diminishing RTFM and simultaneous evidences of diminishing O vacancies clearly indicate that RTFM is driven by defects in oxide lattice and confirms primary role of oxygen vacancies in inducing ferromagnetic ordering in metal oxide semiconductors. The study also provides improved fundamental understanding regarding the ambiguity in the origin of intrinsic RTFM in semiconducting metal oxides and projects their technological application in the field of spintronics. (C) 2013 AIP Publishing LLC.

Evolution of ferromagnetism from a frustrated state in LixNi(2-x)O2 (0.67 < x < 0.98)

Two-dimensional triangular-lattice antiferromagnetic systems continue to be an interesting area in condensed matter physics and LiNiO2 is one such among them. Here we present a detailed experimental magnetic study of the quasi-stoichiometric LixNi2-xO2 system (0.67ordering temperature is observed. Most strikingly, with the Li deficiency the nature of the magnetic ground state is changed from spin glass to ferromagnetic, with two intermediate states-namely cluster glass and re-entrant spin glass. The critical behaviour of the re-entrant spin glass is also studied here. The critical exponents (beta, gamma and delta) are extracted from the modified Arrot plot, Kouvel-Fisher method, and critical isotherm analysis. The critical exponents match with the long-range mean-field model. The values of the critical exponents are confirmed by the Widom scaling law: delta = 1 + gamma beta(-1). Furthermore, the universality class of the scaling relations is verified, where the scaled m and scaled h collapse into two branches. Finally, based on our observations, a phase diagram is constructed.

Local structural disorder and its influence on the average global structure and polar properties in Na0.5Bi0.5TiO3

Na0.5Bi0.5TiO3 (NBT) and its derivatives have prompted a great surge in interest owing to their potential as lead-free piezoelectrics. In spite of five decades since its discovery, there is still a lack of clarity on crucial issues such as the origin of significant dielectric relaxation at room temperature, structural factors influencing its depoling, and the status of the recently proposed monoclinic (Cc) structure vis-a-vis the nanosized structural heterogeneities. In this work, these issues are resolved by comparative analysis of local and global structures on poled and unpoled NBT specimens using electron, x-ray, and neutron diffraction in conjunction with first-principles calculation, dielectric, ferroelectric, and piezoelectric measurements. The reported global monoclinic (Cc) distortion is shown not to correspond to the thermodynamic equilibrium state at room temperature. The global monocliniclike appearance rather owes its origin to the presence of local structural and strain heterogeneities. Poling removes the structural inhomogeneities and establishes a long-range rhombohedral distortion. In the process the system gets irreversibly transformed from a nonergodic relaxor to a normal ferroelectric state. The thermal depoling is shown to be associated with the onset of incompatible in-phase tilted octahedral regions in the field-stabilized long range rhombohedral distortion.

Long ranged structural modulation in the pre-morphotropic phase boundary cubic-like state of the lead-free piezoelectric Na1/2Bi1/2TiO3-BaTiO3

The nature of the pre-morphotropic phase boundary (MPB) cubic-like state in the lead-free piezoelectric ceramics (1-x)Na1/2Bi1/2TiO3-(x)BaTiO3 at x similar to 0.06 has been examined in detail by electric field and temperature dependent neutron diffraction, x-ray diffraction, dielectric and ferroelectric characterization. The superlattice reflections in the neutron diffraction patterns cannot be explained with the tetragonal P4bm and the rhombohedral (R3c) phase coexistence model. The cubic like state is rather a result of long ranged modulated complex octahedral tilt. This modulated structure exhibits anomalously large dielectric dispersion. The modulated structure transforms to a MPB state on poling. The field-stabilized MPB state is destroyed and the modulated structure is restored on heating the poled specimen above the Vogel-Fulcher freezing temperature. The results show the predominant role of competing octahedral tilts in determining the nature of structural and polar states in Na1/2Bi1/2TiO3-based ferroelectrics. (C) 2013 AIP Publishing LLC.

Minimizing the Complexity of Fast Sphere Decoding of STBCs

Decoding of linear space-time block codes (STBCs) with sphere-decoding (SD) is well known. A fast-version of the SD known as fast sphere decoding (FSD) was introduced by Biglieri, Hong and Viterbo. Viewing a linear STBC as a vector space spanned by its defining weight matrices over the real number field, we define a quadratic form (QF), called the Hurwitz-Radon QF (HRQF), on this vector space and give a QF interpretation of the FSD complexity of a linear STBC. It is shown that the FSD complexity is only a function of the weight matrices defining the code and their ordering, and not of the channel realization (even though the equivalent channel when SD is used depends on the channel realization) or the number of receive antennas. It is also shown that the FSD complexity is completely captured into a single matrix obtained from the HRQF. Moreover, for a given set of weight matrices, an algorithm to obtain an optimal ordering of them leading to the least FSD complexity is presented. The well known classes of low FSD complexity codes (multi-group decodable codes, fast decodable codes and fast group decodable codes) are presented in the framework of HRQF.

Size dependent structural relaxations and dielectric properties induced by surface functionalized MWNTs in poly(vinylidene fluoride)/poly(methyl methacrylate) blends

Structural dynamics, dielectric permittivity and ferroelectric properties in poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) (PVDF/PMMA) blends with respect to crystalline morphology was systematically investigated in presence of amine functionalized MWNTs (NH2-MWNTs) using dielectric spectroscopy. The crystalline morphology and the crystallization driven demixing in the blends was assessed by light microscopy (LM), wide angle X-ray diffraction (WXRD) and, in situ, by shear rheology. The crystal nucleation activity of PVDF was greatly induced by NH2-MWNTs, which also showed two distinct structural relaxations in dielectric loss owing to mobility confinement of PVDF chains and smaller cooperative lengths. The presence of crystal-amorphous interphase was supported by the presence of interfacial polarization at lower frequencies in the dielectric loss spectra. On contrary, the control blends showed a single broad relaxation at higher frequency due to defective crystal nuclei. This was further supported by monitoring the dielectric relaxations during isothermal crystallization of PVDF in the blends. These observations were addressed with respect to the spherulite sizes which were observed to be larger in case of blends with NH2-MWNTs. Higher dielectric permittivity with minimal losses was also observed in blends with NH2-MWNTs as compared to neat PVDF. Polarization obtained using P-E (polarization-electric field) hysteresis loops was higher in case of blends with NH2-MWNTs in contrast to control blends and PVDF. These observations were corroborated with the charge trapped at the crystal-amorphous interphase and larger crystal sizes in the blends with NH2-MWNTs. The microstructure and localization of MWNTs were assessed using SEM.

Magnetic Structure and Properties of the Rechargeable Battery Insertion Compound Na2FePO4F

The magnetic structure and properties of sodium iron fluorophosphate Na2FePO4F (space group Pbcn), a cathode material for rechargeable batteries, were studied using magnetometry and neutron powder diffraction. The material, which can be described as a quasi-layered structure with zigzag Fe-octahedral chains, develops a long-range antiferromagnetic order below similar to 3.4 K. The magnetic structure is rationalized as a super-exchange-driven ferromagnetic ordering of chains running along the a-axis, coupled antiferromagnetically by super-super-exchange via phosphate groups along the c-axis, with ordering along the b-axis likely due to the contribution of dipole dipole interactions.

Anomalous magnetism of Pr in PrCoAsO

Detailed magnetization and magneto-transport measurements studies are carried out to unearth the anomalous magnetism of Pr in PrCoAsO compound. The studied PrCoAsO sample is single phase and crystallized in the tetragonal structure with space group P4/nmm in analogy of ZrCuSiAs type compounds. Detailed magnetization measurements showed that Co moments in PrCoAsO exhibit weakly itinerant ferromagnetic Co spins ordering at below 80 K with a small magnetic moments of similar to 0.12 mu B/f.u. High temperatures Curie-Weiss fit, resulted in effective paramagnetic moment mu(eff) (exp) of 5.91 mu(B)/f.u., which can be theoretically assigned to 3d Co (3.88 mu(B)) and 4f Pr (3.58 mu(B)). Further, a positive Curie-Weiss temperature (Theta) of 136 K is seen, indicating predominant ferromagnetic interactions in PrCoAsO. Detailed transport measurements showed that PrCoAsO exhibit metallic behavior and negative magneto-resistance below ferro-magnetically (FM) ordered state. Surprisingly, the situation of PrCoAsO is similar to non magnetic La containing LaCoAsO and strikingly different than that as reported for magnetic Nd, Sm and Gd i.e., (Nd/Sm/Gd)CoAsO. The magnetic behavior of PrCoAsO being closed to LaCoAsO and strikingly different to that of (Nd/Sm/Gd)CoAsO is unusual. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

A structural and spectroscopic investigation of reduced graphene oxide under high pressure

The effect of high pressure on reduced graphene oxide (RGO) has been investigated using X-ray diffraction (XRD) and infrared (IR) absorption spectroscopy. Our XRD measurements show two-step reversible compression in the inter-layer spacing of RGO whereas intra-layer ordering exhibits a high pressure behavior similar to that of graphite up to 20 GPa. The line shape analysis of (100) peak, representing the intra-layer ordering, suggests presence of local out of plane distortions in RGO in the form of puckered regions which progressively straighten out as a function of pressure. IR measurements show reversible changes in spectroscopic features attributed to remnant functional groups in the inter-layer region. These measurements suggest high stability and recovering ability of RGO under pressure cycling. (C) 2014 Elsevier Ltd. All rights reserved.

Reentrant Superspin Glass Phase in a La0.82Ca0.18MnO3 Ferromagnetic Insulator

We report results of the magnetization and ac susceptibility measurements down to very low fields on a single crystal of the perovskite manganite, La-0.82 Ca-0.18 MnO3. This composition falls in the intriguing ferromagnetic insulator region of the manganite phase diagram. In contrast to earlier beliefs, our investigations reveal that magnetically (and in every other sense), this is a single- phase system with a ferromagnetic ordering temperature of around 170 K. However, this ferromagnetic state is magnetically frustrated, and the system exhibits pronounced glassy dynamics below 90 K. Based on measured dynamical properties, we propose that this quasi-long-ranged ferromagnetic phase, and the associated superspin glass behavior, is the true magnetic state of the system, rather than being a macroscopic mixture of ferromagnetic and antiferromagnetic phases, as often suggested. Our results provide an understanding of the quantum phase transition from an antiferromagnetic insulator to a ferromagnetic metal via this ferromagnetic state as a function of x in La1-xCaxMnO3, in terms of the possible formation of magnetic polarons.

Temperature dependent magnetic, dielectric and Raman studies of partially disordered La2NiMnO6

We report a detailed magnetic, dielectric and Raman studies on partially disordered and biphasic double perovskite La2NiMnO6. DC and AC magnetic susceptibility measurements show two magnetic anomalies at T-C1 similar to 270 K and T-C2 similar to 240 K, which may indicate the ferromagnetic ordering of the monoclinic and rhombohedral phases, respectively. A broad peak at a lower temperature (T-sg similar to 70 K) is also observed indicating a spin-glass transition due to partial anti-site disorder of Ni2+ and Mn4+ ions. Unlike the pure monoclinic phase, the biphasic compound exhibits a broad but a clear dielectric anomaly around 270 K which is a signature of magneto-dielectric effect. Temperature-dependent Raman studies between the temperature range 12-300 K in a wide spectral range from 220 cm(-1) to 1530 cm(-1) reveal a strong renormalization of the first as well as second-order Raman modes associated with the (Ni/Mn)O-6 octahedra near T-C1 implying a strong spin-phonon coupling. In addition, an anomaly is seen in the vicinity of spin-glass transition temperature in the temperature dependence of the frequency of the anti-symmetric stretching vibration of the octahedra. (C) 2014 Elsevier Ltd. All rights reserved.

Formation and Thermal Stability of Gold-Silica Nanohybrids: Insight into the Mechanism and Morphology by Electron Tomography

Gold-silica hybrids are appealing in different fields of applications like catalysis, sensorics, drug delivery, and biotechnology. In most cases, the morphology and distribution of the heterounits play significant roles in their functional behavior. Methods of synthesizing these hybrids, with variable ordering of the heterounits, are replete; however, a complete characterization in three dimensions could not be achieved yet. A simple route to the synthesis of Au-decorated SiO2 spheres is demonstrated and a study on the 3D ordering of the heterounits by scanning transmission electron microscopy (STEM) tomography is presentedat the final stage, intermediate stages of formation, and after heating the hybrid. The final hybrid evolves from a soft self-assembled structure of Au nanoparticles. The hybrid shows good thermal stability up to 400 degrees C, beyond which the Au particles start migrating inside the SiO2 matrix. This study provides an insight in the formation mechanism and thermal stability of the structures which are crucial factors for designing and applying such hybrids in fields of catalysis and biotechnology. As the method is general, it can be applied to make similar hybrids based on SiO2 by tuning the reaction chemistry as needed.

Evolution of superconductivity in PrFe1-xCoxAsO (x=0.0-1.0)

We report the synthesis and physical property characterization of Prfe(1-x)Co(x)AsO (x=0.0-1.0). The studied samples are synthesized by through the solid state reaction route via the vacuum encapsulation method. The pristine compound PrFeAsO does not show superconductivity, but rather exhibits a metallic step like transition due to spin density wave (SOW) ordering of Fe moments (Fe-SDW) below 150 K, Followed by another upward step due to anomalous ordering of Pr moments (Pr-TN) at 12 K. Both the Fe-SDW and Pr-TN temperatures decrease monotonically with Co substitution at Fe site Superconductivity appears in a narrow range of x from 0.07 to 0.25 with maximum T-c at 11.12 K for x=0.15. Samples with x >= 0.25 exhibit metallic behavior right from 300 K down to 2 K, without any Fe-SDW or Pr-TN steps in resistivity. In fact, though Fe-SDW decreases monotonically, the pr(TN) disappeared even with x=0.02. The magneto transport measurements below 14 Ton superconducting polycrystalline Co doped Pi FeAs0 lead to extrapolated values of the upper critical fields H-c2(0)] of up to 60 T. (C) 2014 Elsevier Ltd. All rights reserved.

Dynamics of a driven magneto-martensitic ribbon

We investigate the dynamics of a sinusoidally driven ferromagnetic martensitic ribbon by adopting a recently introduced model that involves strain and magnetization as order parameters. Retaining only the dominant mode of excitation we reduce the coupled set of partial differential equations for strain and magnetization to a set of coupled ordinary nonlinear equations for the strain and magnetization amplitudes. The equation for the strain amplitude takes the form of parametrically driven oscillator. Finite strain amplitude can only be induced beyond a critical value of the strength of the magnetic field. Chaotic response is seen for a range of values of all the physically interesting parameters. The nature of the bifurcations depends on the choice of temperature relative to the ordering of the Curie and the martensite transformation temperatures. We have studied the nature of response as a function of the strength and frequency of the magnetic field, and magneto-elastic coupling. In general, the bifurcation diagrams with respect to these parameters do not follow any standard route. The rich dynamics exhibited by the model is further illustrated by the presence of mixed mode oscillations seen for low frequencies. The geometric structure of the mixed mode oscillations in the phase space has an unusual deep crater structure with an outer and inner cone on which the orbits circulate. We suggest that these features should be seen in experiments on driven magneto-martensitic ribbons. (C) 2014 Elsevier B. V. All rights reserved.

Biomimetic molecular organization of naphthalene diimide in the solid state: tunable (chiro-) optical, viscoelastic and nanoscale properties

The interfacing of aromatic molecules with biomolecules to design functional molecular materials is a promising area of research. Intermolecular interactions determine the performance of these materials and therefore, precise control over the molecular organization is necessary to improve functional properties. Herein we describe the tunable biomimetic molecular engineering of a promising n-type organic semiconductor, naphthalene diimide (NDI), in the solid state by introducing minute structural mutations in the form of amino acids with variable Ca-functionality. For the first time we could achieve all four possible crystal packing modes, namely cofacial, brickwork, herringbone and slipped stacks of the NDI system. Furthermore, amino acid conjugated NDIs exhibit ultrasonication induced organogels with tunable visco-elastic and temperature responsive emission properties. The amino acid-NDI conjugates self-assemble into 0D nanospheres and 1D nanofibers in their gel state while the ethylamine-NDI conjugate forms 2D sheets from its solution. Photophysical studies indicated the remarkable influence of molecular ordering on the absorption and fluorescence properties of NDIs. Interestingly, the circular dichroism (CD) and X-ray diffraction (XRD) studies revealed the existence of helical ordering of NDIs in both solution and solid state. The chiral amino acids and their conformations with respect to the central NDI core are found to influence the nature of the helical organization of NDIs. Consequently, the origin of the preferential handedness in the helical organization is attributed to transcription of chiral information from the amino acid to the NDI core. On account of these unique properties, the materials derived from NDI-conjugates might find a wide range of future interdisciplinary applications from materials to biomedicine.