Origin of ferroelectricity in cubic phase of Hf substituted BaTiO3.

The origin of ferroelectricity in the cubic phase of BaTi1-xHfxO3has been investigated. The presence of well-defined ferroelectric polarization versus electric field (PE) hysteresis loop in the samples with global cubic symmetry suggests the presence of 'local polar regions', induced possibly due to the huge difference in the electronegativity and also difference in the ionic radii of Hf+4and Ti+4ions, which may lead to local structural disorder. The presence of polar regions is also supported through the appearance of A1(TO) polar mode in Raman spectra which in principle should be absent in the samples with cubic symmetry. The results are discussed in terms of disorder-induced local dipoles due to the electronegativity difference between Hf and Ti ions.

Ni-Doped ZnO Thin Films: Deposition, Characterization and Photocatalytic Applications.

Root like structured Ni-doped zinc oxide [Zn(1-x)NixO (x = 0.09)] thin films were deposited on a non-conducting glass substrate by indigenously developed spray pyrolysis system at optimized substrate hotness of 573±5 K. Thus obtained Ni-doped ZnO thin films were characterized by UV-visible spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Atomic Force Microscopy (AFM). XRD result revealed that Ni-doped ZnO has a polycrystalline nature with a hexagonal wurtzite structure. For pure ZnO and Ni-doped ZnO thin films, the particle sizes were 60.9 and 53.3 nm while lattice strain values were 1.56×10-3 and 1.14×10-3, respectively. The film surface showed characteristic root-like structure as observed by the SEM. It was observed that the Ni-doped ZnO thin films were grown in high density along with more extent of branching as compared to pure ZnO thin films but retained the root-like morphologies, however, the branches were more-thinner and of shorter lengths. AFM analysis showed that the surface grains of the Ni-doped samples are homogeneous with less RMS roughness values compared with the undoped ZnO samples. The photocatalytic activity of the prepared thin films was evaluated by the degradation of methyl orange (MO) dye under UV light irradiation. Pure ZnO and Ni-doped ZnO thin films took 150 min and 100 min to degrade about 60% MO dye, respectively.

Synthesis, local structure and optical property studies of α-SnS microrods by synchrotron X-ray pair distribution function and micro-Raman shift.

A hydrothermal synthesis method was employed for the preparation of tin sulfide (α-SnS) microrod samples (SnS-A and SnS-B) using ethylenediamine and deionized water as the surfactant at ratios from 50 : 50 to 100 : 00. The atomic structures of the α-SnS microrods were studied using atomic pair distribution function (PDF) analysis and total synchrotron X-ray scattering data. The synchrotron X-ray diffraction (ScXRD) patterns and PDF data reveal that the structure of the SnS microrods is orthorhombic. From the refinement of the PDF, the first and second peaks correspond to nearest (Sn2+-S2-) and second nearest distances (Sn2+-Sn2+) of 2.546 (0.003) Å and 4.106 (0.004) Å, and 2.527 (0.005) Å and 4.087 (0.006) Å for SnS-A and SnS-B samples, respectively. The TEM results show that samples SnS-A and SnS-B have a microrod structure, with microrod diameters of 800 nm and 500 nm with lengths of tens of micrometers, respectively. The SnS-A and SnS-B samples show a direct band gap of 1.6 eV and 2 eV, respectively, using the Kubelka-Munk transformation of the UV-visible spectra. The micro-Raman spectra of the SnS-A and SnS-B microrods exhibited an Ag mode of SnS at 228.4 and 223 cm-1, respectively. The second peaks at 306.7, and 309 cm-1 are associated with the secondary phases of the SnS2 phase, whereas the third broad peaks at 616.5, and 613 cm-1 revealed that there was a deformation mode of sulfate in the SnS-A and SnS-B samples.

Thermoelectric properties of Ag-doped CuS nanocomposites synthesized by a facile polyol method.

We report the first thermoelectric properties of Cu1-xAgxS, x = 0-0.75 nanocomposites, synthesized by using a facile polyol method. Systematic characterizations using powder XRD, Rietveld refinement of XRD, EDAX, XPS and Raman spectroscopy confirmed their single phase, hexagonal crystal structure with the space group P63/mmc, nominal elemental composition, valence states of the constituent elements and stoichiometric nature. The TEM images showing the CuS formation of nearly perfect hexagonal disk-like particles of average thickness 26.7 nm and breadth ranging in a few hundreds of nanometers with nanorods stacked from these hexagonal nanodisks (NDs) elongated along the c axis corroborate the FESEM images. Attributed to structural phase transition, an anomaly at 55 K is clearly observed in both the thermopower and Hall resistivity data. By increasing x, a systematic reduction in thermal conductivity was observed near 300 K. Consequently, a 50% enhancement in figure of merit was observed for Cu0.9Ag0.1S as compared to pure CuS at 300 K. These results therefore are expected to provide a new direction in improving ZT near 300 K.

Low-temperature high magnetic field powder x-ray diffraction setup for field-induced structural phase transition studies from 2 to 300 K and at 0 to 8-T field.

A low-temperature and high magnetic field powder x-ray diffractometer (XRD) has been developed at UGC-DAE CSR (UGC: University Grant Commission, DAE: Department of Atomic Energy, and CSR: Consortium for scientific research), Indore, India. The setup has been developed around an 18 kW rotating anode x-ray source delivering Cu-Kα x-rays coming from a vertical line source. It works in a symmetric θ-2θ parallel beam geometry. It consists of a liquid helium cryostat with an 8 T split-pair Nb-Ti superconducting magnet comprising two x-ray windows each covering an angular range of 65°. This is mounted on a non-magnetic type heavy duty goniometer equipped with all necessary motions along with data collection accessories. The incident x-ray beam has been made parallel using a parabolic multilayer mirror. The scattered x-ray is detected using a NaI detector through a 0.1° acceptance solar collimator. To control the motions of the goniometer, a computer programme has been developed. The wide-angle scattering data can be collected in a range of 2°-115° of 2θ with a resolution of ∼0.1°. The whole setup is tightly shielded for the scattered x-rays using a lead hutch. The functioning of the goniometer and the artifacts arising possibly due to the effect of stray magnetic field on the goniometer motions, on the x-ray source, and on the detector have been characterized by collecting powder XRD data of a National Institute of Standards and Technology certified standard reference material LaB6 (SRM-660b) and Si powder in zero-field and in-field conditions. Occurrence of field induced structural-phase transitions has been demonstrated on various samples like Pr0.5Sr0.5MnO3, Nd0.49Sr0.51MnO3-δ and La0.175Pr0.45Ca0.375MnO3 by collecting data in zero field cool and field cool conditions.

Displacive-type ferroelectricity from magnetic correlations within spin-chain.

Observation of ferroelectricity among non-d(0) systems, which was believed for a long time an unrealistic concept, led to various proposals for the mechanisms to explain the same (i.e. magnetically induced ferroelectricity) during last decade. Here, we provide support for ferroelectricity of a displacive-type possibly involving magnetic ions due to short-range magnetic correlations within a spin-chain, through the demonstration of magnetoelectric coupling in a Haldane spin-chain compound Er2BaNiO5 well above its Néel temperature of (TN = ) 32 K. There is a distinct evidence for electric polarization setting in near 60 K around which there is an evidence for short-range magnetic correlations from other experimental methods. Raman studies also establish a softening of phonon modes in the same temperature (T) range and T-dependent x-ray diffraction (XRD) patterns also reveal lattice parameters anomalies. Density-functional theory based calculations establish a displacive component (similar to d(0)-ness) as the root-cause of ferroelectricity from (magnetic) NiO6 chain, thereby offering a new route to search for similar materials near room temperature to enable applications.

Kinetic arrest of the first-order to R3c Pbnm phase transition in supercooled La(x)MnO(3+δ) (x = 1 and 0.9).

We report the occurrence of kinetic arrest of the first-order phase transition from R3c to Pbnm in supercooled La(x)MnO(3±Î´) (x = 1 and 0.9, i.e. δ > 0.125). Structural studies have been done, employing low temperature transmission electron microscopy (LT-TEM) and low temperature x-ray diffraction (LT-XRD) techniques. No phase transformation was observed even in La(x)MnO(3±Î´) aged for ~12 h at 98 K. The evidence of the occurrence of kinetic arrest was realized at low temperatures through in situ electron beam triggered nucleation and perpetual devitrification of the R3c phase into a Pbnm phase. It was clearly evidenced that the R3c structure of La(x)MnO(3±Î´), below its ferromagnetic transition temperature, is metastable and prone to be transformed to a Pbnm orthorhombic structure following initiation by an electron beam trigger. The electron beam transformed Pbnm phase was found to transform back to the R3c phase through a first-order phase transition occurring close to the ferromagnetic to paramagnetic transition (T(c)) during heating. The glass-like kinetics of the arrested R3c phase has been investigated through resistance relaxation measurements, showing a decreasing logarithmic rate of decay of the arrested R3c phase towards the stable Pbnm phase with decreasing temperature, down to 5 K. On the basis of the correlations observed in the resistance-versus-temperature, magnetization-versus-temperature, magnetization-versus-field, resistance relaxation and LT-XRD measurements, the occurrence of kinetic arrest has been attributed to the suppression of Jahn-Teller distortion by double exchange across the insulator-metal transition.

Nanoparticle induced piezoelectric, super toughened, radiation resistant, multi-functional nanohybrids.

We have developed multifunctional nanohybrids of poly(vinylidene fluoride-co-chlorotrifluoroethylene) (CTFE) with a small percentage of surface modified inorganic layered silicate showing dramatic improvement in toughness, radiation resistant and piezoelectric properties vis-à-vis pristine polymer. Massive intercalation (d(001) 1.8 → 3.9 nm) of polymer inside the nanoclay galleries and unique crystallization behavior of the fluoropolymer on the surface of individual silicate layer has been reported. Toughness in the nanohybrid increases more than three orders of magnitude as compared to pure CTFE. High energy radiation (80 MeV Si(+7)) causes chain session, amorphization and creates olefinic bonds in the pure polymer while the nanohybrids are radiation resistant at a similar dose. Nanoclay induces the metastable piezoelectric ß-phase in CTFE, suitable for sensor and actuator application. Molecular level changes after irradiation and controlled morphology for smart membrane have been confirmed by using spectroscopy, sol-gel technique, surface morphology studies and in situ residual gas analysis.

High coercive field and magnetization reversal in core-shell cum nanotwin driven Ni/NiO nanospheres.

We report here nanotwin-core-shell Ni(core)NiO(shell) spheres of average size 25 nm prepared through polyol method. They exhibit high coercive field at 2 K, sharp peak at approximately 20 K in magnetization curve and magnetization reversal. Interestingly, exchange bias due to antiferromagnetic NiO shell is absent. Among other possibilities, anisotropy variations due to particle size distribution and twinning associated with disorder appear to play an important role. Further, magnetic interactions of twinned bigger spheres, which may also act as superferrimagnetic-like Ni multilayer cores, with superparamagnetic Ni of smaller spheres, might be the additional causes. These nanostructures therefore seem to have potential interest in memory effect.

Synthesis and characterization of Ag-polymer nanocomposites.

We report the synthesis of Ag nanoparticles in polyethylene terephthalate (PET) matrix using atom beam co-sputtering. Metal filling factor was evaluated by Rutherford backscattering spectrometry. Microstructural evolutions of the nanocomposites films were investigated by transmission electron microscopy, which confirmed the formation of irregular shaped Ag nanoparticles. The X-ray photoelectron spectroscopy measurements of the sputter deposited PET film and co-sputtered deposited Ag-PET as well as PET bulk foil (from Goodfellows) were performed to study chemical composition of the nanocomposite films. The optical properties of these nanocomposites were studied by light absorption/transmission, which revealed a narrow transmission of UV light approximately 320 nm and a broad surface plasmon resonance absorption extending up to infrared region (approximately 2400 nm). Swift heavy ion irradiation of Ag-PET nanocomposite resulted in narrowing the full width at half maximum of transmission band.