Parasmani Rajput

Size effect on electronic sputtering of LiF thin films

Electronic sputtering in polycrystalline LiF thin film by 120MeV Ag25+ is investigated. The sputter yields of Li and F for the different thicknesses (10–265nm) of films are measured with online elastic recoil detection analysis technique. A reduction in sputter yield, from ∼2.3×106 to 2.2×104 atoms/ion, is observed with increase in the film thickness. The trend in the experimental results can be explained in terms of size effect in thin film following inelastic thermal spike model. The confinement of energy in the film having smaller grains and lower thickness results in higher temperature causing higher sputtering yield.

Inverse magnetocaloric effect in Mn2NiGa and Mn1.75Ni1.25Ga magnetic shape memory alloys

Inverse magnetocaloric effect is demonstrated in Mn2NiGa and Mn1.75Ni1.25Ga magnetic shape memory alloys. The entropy change at the martensite transition is larger in Mn1.75Ni1.25Ga, and it increases linearly with magnetic field in both the specimens. Existence of inverse magnetocaloric effect is consistent with the observation that magnetization in the martensite phase is smaller than the austenite phase. Although the Mn content is smaller in Mn1.75Ni1.25Ga, from neutron diffraction, we show that the origin of inverse magnetocaloric effect is the antiferromagnetic interaction between the Mn atoms occupying inequivalent sites.

Modulated structure in the martensite phase of Ni1.8Pt0.2MnGa: A neutron diffraction study

7M orthorhombic modulated structure in the martensite phase of Ni1.8Pt0.2MnGa is reported by powder neutron diffraction study, which indicates that it is likely to exhibit magnetic field induced strain. The change in the unit cell volume is less than 0.5% between the austenite and the martensite phases, as expected for a volume conserving martensite transformation. The magnetic structure analysis shows that the magnetic moment in the martensite phase is higher compared to Ni2MnGa, which is in good agreement with magnetization measurement.

Search for Origin of Room Temperature Ferromagnetism Properties in Ni-Doped ZnO Nanostructure

The origin of room temperature (RT) ferromagnetism (FM) in Zn1-xNixO (0< x < 0.125) samples are systematically investigated through physical, optical, and magnetic properties of nanostructure, prepared by simple low-temperature wet chemical method. Reitveld refinement of X-ray diffraction pattern displays an increase in lattice parameters with strain relaxation and contraction in Zn/O occupancy ratio by means of Ni-doping. Similarly, scanning electron microscope demonstrates modification in the morphology from nanorods to nanoflakes with Ni doping, suggests incorporation of Ni ions in ZnO. More interestingly, XANES (X-ray absorption near edge spectroscopy) measurements confirm that Ni is being incorporated in ZnO as Ni2+. EXAFS (extended X-ray absorption fine structure) analysis reveals that structural disorders near the Zn sites in the ZnO samples upsurges with increasing Ni concentration. Raman spectroscopy exhibits additional defect driven vibrational mode (at 275 cm-1), appeared only in Ni-doped samples and the shift with broadening in 580 cm-1 peak, which manifests the presence of the oxygen vacancy (VO) related defects. Moreover, in photoluminescence (PL) spectra, we have observed a peak at 524 nm, indicating the presence of singly ionized VO+, which may be activating bound magnetic polarons (BMPs) in dilute magnetic semiconductors (DMSs). Magnetization measurements indicate weak ferromagnetism at RT, which rises with increasing Ni concentration. It is therefore proposed that the effect of the Ni ions as well as the inherent exchange interactions arising from VO+ assist to produce BMPs, which are accountable for the RT-FM in Zn1-xNixO (0< x < 0.125) system.

Observation of large dielectric permittivity and dielectric relaxation phenomenon in Mn-doped lanthanum gallate

Polycrystalline LaGa1−xMnxO3 (x = 0, 0.05, 0.1, 0.15, 0.2 and 0.3) samples were prepared via the solid-state reaction method. These samples were characterized using synchrotron-based X-ray diffraction (XRD) and the X-ray absorption near edge structure (XANES). XRD studies confirm the orthorhombic structure for the prepared samples whereas XANES analysis reveals the co-existence of Mn3+ and Mn4+ in all Mn-doped samples. Dielectric relaxation is observed for all Mn-doped samples whereas a large dielectric constant (e′) is perceived in samples with higher Mn doping (x = 0.2 and x = 0.3). Occurrence of a large e′ is attributed to the huge decrease in impedance with increasing Mn doping which is governed by the hopping charge transport and extrinsic interface effects, whereas at high frequencies, this effect is observed possibly due to dipolar effects associated with the possible off-centrosymmetry of the MnO6 octahedron which is indicated by the pre-edge feature (Mn K-edge) in XANES and validated through P–E measurements. The appearance of dielectric relaxation was credited to the dipolar effects associated with the flipping of the Mn3+/Mn4+ dipole i.e., with the hopping of charge carriers between Mn3+ and Mn4+ under an external electric field. The value of activation energy (Ea = 0.36 eV), extracted from temperature-dependent dielectric data, reveals the polaron hopping mechanism.

Observation of room temperature magnetodielectric effect in Mn-doped lanthanum gallate and study of its magnetic properties

Polycrystalline samples of Mn-doped LaGa1−xMnxO3 (LGMO) with 0 ≤ x ≤ 0.2 have been prepared via solid-state reaction method. The structural phase purity of all these samples was confirmed by powder X-ray diffraction experiments carried out at the BL-12 beamline of the Indus-2 synchrotron radiation source. Room-temperature (RT) dielectric measurements were performed in the absence and presence of a magnetic field. A noticeable magnetodielectric (MD) effect, i.e., a change in the value of the dielectric constant owing to the application of a low magnetic field, was observed in the LGMO sample with x = 0.2 (LG8M2O). In order to separate the intrinsic and resistive contributions present in the observed RT MD effect, magnetoresistance impedance spectroscopy (MRIS) was performed at RT. The present MRIS analysis suggests that at frequencies corresponding to the grain contribution (≥105 Hz for the present samples), the observed MD phenomenon appears to be an intrinsic property of the presently studied samples, whereas at lower probing frequencies (<105 Hz) the observed change appears to be dominated by MR (considering frequency-dependent resistance), which was possibly due to the coexistence of Mn3+ and Mn4+. The coexistence of Mn3+ and Mn4+ was revealed by XANES (Mn K-edge) spectroscopy. Moreover, RT and low-temperature magnetization–magnetic field (M–H) measurements, along with M–T measurements in FC and ZFC modes, were performed to investigate the state of magnetic ordering. The appearance of a narrow M–H loop indicates the presence of some magnetic ordering at RT. Furthermore, a ferromagnetic (FM) transition observed around 36 K and a normal M–H loop with saturated magnetization recorded at 5 K confirm FM ordering at low temperatures, whereas a bifurcation in FC-ZFC curves indicates competing FM and antiferromagnetic (AFM) interactions at low temperatures.

Origin of anomalous diffusion in iron mononitride thin films

We have studied the origin of a counter intuitive diffusion behavior of Fe and N atoms in a iron mononitride (FeN) thin film. It was observed that in-spite of a larger atomic size, Fe tend to diffuse more rapidly than smaller N atoms. This only happens in the N-rich region of Fe-N phase diagram, in the N-poor regions, N diffusion coefficient is orders of magnitude larger than Fe. Detailed self-diffusion measurements performed in FeN thin films reveal that the diffusion mechanism of Fe and N is different - Fe atoms diffuse through a complex process, which in addition to a volume diffusion, pre-dominantly controlled by a fast grain boundary diffusion. On the other hand N atoms diffuse through a classical volume-type diffusion process. Observed results have been explained in terms of stronger Fe-N (than Fe-Fe) bonds generally predicted theoretically for mononitride compositions of transition metals.

Investigating structural aspects to understand the putative/claimed non-toxicity of the Hg-based Ayurvedic drug Rasasindura using XAFS.

XANES- and EXAFS-based analysis of the Ayurvedic Hg-based nano-drug Rasasindura has been performed to seek evidence of its non-toxicity. Rasasindura is determined to be composed of single-phase α-HgS nanoparticles (size ∼24 nm), free of Hg(0) or organic molecules; its structure is determined to be robust (<3% defects). The non-existence of Hg(0) implies the absence of Hg-based toxicity and establishes that chemical form, rather than content of heavy metals, is the correct parameter for evaluating the toxicity in these drugs. The stable α-HgS form (strong Hg-S covalent bond and robust particle character) ensures the integrity of the drug during delivery and prevention of its reduction to Hg(0) within the human body. Further, these comparative studies establish that structural parameters (size dispersion, coordination configuration) are better controlled in Rasasindura. This places the Ayurvedic synthesis method on par with contemporary techniques of nanoparticle synthesis.

Micro-Raman and electronic structure study on kinetics of electronic excitations induced monoclinic-to-tetragonal phase transition in zirconium oxide films

Monoclinic-to-tetragonal phase transformation (PT) in sputtering grown zirconium oxide (ZrO2) films on silicon substrates by electronic excitation (EE) induced by swift heavy ion (SHI) irradiation is reported. The density of EEs and the fluences of irradiation were varied for the better insight of phase transformation kinetics. The phase transition is well evident from the investigations using grazing incidence X-ray diffraction (GIXRD) and micro-Raman spectroscopy (mRS). Studies reveal a PT from the monoclinic to tetragonal phase. It is noted that at high fluence of Ag ion irradiation partly PT to cubic phase is also observed. However, it is clear from this study that this PT is not only due to transient temperature induced by SHI, but also attributed to the strain in the lattice created under the influence of the induced density of defects in the lattice. Interestingly, it may be noted that strain is well evident by the stiffening of the characteristic Raman modes of monoclinic phase. The modifications in electronic and local structure revealed using soft X-ray absorption spectroscopy (XAS) and X-ray absorption fine structure (XAFS) and found after fitting of Zr K-edge XAFS that phase transformation from m-ZrO2 to t-ZrO2 and/or c-ZrO2 upon Ni and Ag irradiation. Studies would elucidate a deeper understanding about the kinetics of PT under such non-equilibrium conditions.

Investigation on stability and leaching characteristics of mixtures of biogenic arsenosulphides and iron sulphides formed under reduced conditions

Arsenic is removed from aqueous phase through precipitation as arsenosulphides and/or co-precipitation and adsorption on iron sulphides. Studies were carried out to ascertain the stability of reduced biogenic arsenic and iron sulphide precipitates formed in an attached growth reactor (AGR) through a series of experiments based on Toxicity Characteristic Leaching Procedure (TCLP), aging and long term leaching tests. About half of the AGR was initially added with waste activated carbon (WAC) to support the growth of mixed microbial consortia and used for treatment of arsenic and iron contaminated simulated groundwater. The X-ray diffraction (XRD), X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy results indicated that the biosolids were mainly composed of arsenosulphides and iron sulphides. While TCLP and aging tests were conducted in anoxic as well as oxic conditions with the aim to evaluate stability of biomass containing biogenic sulphides, long term leaching test was conducted through supply of aerated distilled water to evaluate the stability of spent WAC as well. Results generated from the research indicate that the concentration of leached arsenic never exceeded 123 μg/L under all conditions tested, thus biosolids not imposing an environmental hazard.