Venkata Srinu Bhadram

Spin-phonon coupling in multiferroic RCrO3 (R-Y, Lu, Gd, Eu, Sm): A Raman study

Raman study on a select few orthochromites, RCrO3 (R = Y, Lu, Gd, Eu and Sm), shows that the phonon behavior at TN in compounds with magnetic R-ion (Gd and Sm) is remarkably different from that of non-magnetic R-ion (Y, Lu and Eu). While anomalies in most of the observed phonon frequencies in all these compounds may result from the distortion of CrO6 octahedra due to size effect and magnetostriction arising from Cr-ordering, the anomalous behavior of their linewidths observed at TN for the compounds with only magnetic R-ion suggests spin-phonon coupling. The presence of spin-phonon coupling and the anomalies in the low-frequency modes related to R-ion motion in orthochromites (R = Gd and Sm) support the suggestion that the coupling between 4f-3d moments play an important role in inducing switchable electric polarization.

Contiguous petal-like carbon nanosheet outgrowths from graphite fibers by plasma CVD.

We report a catalyst-free synthesis of cantilevered carbon nanosheet extensions, or petals, from graphite fibers by microwave plasma CVD. Results reveal that the petals grow from the fiber surface layers while preserving graphitic continuity from fiber to the petals. Subtraction of Raman signatures from pristine and decorated fibers reveals a convolution of two underlying peaks at 2687 and 2727 cm−1 that are consistent with profiles of multilayer graphene flakes between 5 and 25 layers. Such structures offer the possibility of minimizing interfacial losses in transport applications, improved interactions with surrounding matrix materials in composites, and a route toward substrate independence for device applications.

Influence of lattice distortion on the Curie temperature and spin-phonon coupling in LaMn0.5Co0.5O3

Two distinct ferromagnetic phases of LaMn(0.5)Co(0.5)O(3) having monoclinic structure with distinct physical properties have been studied. The ferromagnetic ordering temperature T(c) is found to be different for both the phases. The origin of such contrasting characteristics is assigned to the changes in the distance(s) and angle(s) between Mn-O-Co resulting from distortions observed from neutron diffraction studies. Investigations on the temperature dependent Raman spectroscopy provide evidence for such structural characteristics, which affects the exchange interaction. The difference in B-site ordering which is evident from the neutron diffraction is also responsible for the difference in T(c). Raman scattering suggests the presence of spin-phonon coupling for both the phases around the T(c). Electrical transport properties of both the phases have been investigated based on the lattice distortion.

Ion transport mechanism in glasses: non-Arrhenius conductivity and nonuniversal features.

In this article, we report non-Arrhenius behavior in the temperature-dependent dc conductivity of alkali ion conducting silicate glasses well below their glass transition temperature. In contrast to the several fast ion-conducting and binary potassium silicate glasses, these glasses show a positive deviation in the Arrhenius plot. The observed non-Arrhenius behavior is completely reproducible in nature even after prolonged annealing close to the glass transition temperature of the respective glass sample. These results are the manifestation of local structural changes of the silicate network with temperature and give rise to different local environments into which the alkali ions hop, revealed by in situ high-temperature Raman spectroscopy. Furthermore, the present study provides new insights into the strong link between the dynamics of the alkali ions and different sites associated with it in the glasses.

White Light Generation by Carbonyl Based Indole Derivatives Due to Proton Transfer: An Efficient Fluorescence Sensor

The motivation of the present work is to understand the optical, chemical, and electrical aspects of the proton transfer mechanism of indole (I) and some carbonyl based indole derivatives: indole-3-carboxaldehyde (I3C) and indole-7-carboxaldehyde (I7C) for both powder form and their liquid solution. Structural information for indole derivatives (isolated molecule and in solution) is obtained with density functional theory (DFT) and time dependent DFT (TD-DFT) methods. Calculated transition energies are used to generate UV-vis, FTIR, Raman, and NMR spectra which are later verified with the experimental spectra. The occurrence of different conformers [cis (N(c)), trans (N(t)), and zwitterion (Z*)] have been interpreted by Mulliken charge, natural bond orbital (NBO) analysis, and polarization versus electric field (P-E loop) studies. (1)H and (13)C NMR and molecular vibrational frequencies of the fundamental modes established the stability of Nc due to the presence of intramolecular hydrogen bonding (IHB) in the ground state (S0). Computed/experimental UV-vis absorption/emission studies reveal the creation of new species: zwitterion (Z*) and anion (A*) in the excited state (S1) due to excited state intramolecular and intermolecular proton transfer (ESI(ra)PT and ESI(er)PT). Increased electrical conductivity (σ(ac)) with temperature and increased ferroelectric polarization at higher field verifies proton conduction in I7C.

Field-Effect Transistors Based on Thermally Treated Electron Beam-Induced Carbonaceous Patterns

Electron beam-induced carbonaceous deposition (EBICD) derived from residual hydrocarbons in the vacuum chamber has many fascinating properties. It is known to be chemically complex but robust, structurally amorphous, and electrically insulating. The present study is an attempt to gain more insight into its chemical and electrical nature based on detailed measurements such as Raman, XPS, TEM, and electrical. Interestingly, EBIC patterns are found to be blue fluorescent when excited with UV radiation, a property which owes much to sp(2) carbon clusters amidst sp(3) matrix. Temperature-dependent Raman and electrical measurements have confirmed the graphitization of the EBICD through the decomposition of functional groups above 300 °C. Finally, graphitized EBIC patterns have been employed as active p-type channel material in the field-effect transistors to obtain mobilities in the range of 0.2-4 cm(2)/V s.

Effect of pressure on octahedral distortions in RCrO3 (R?=?Lu, Tb, Gd, Eu, Sm): the role of R-ion size and its implications

The effect of rare-earth ion size on the octahedral distortions in rare-earth chromites (RCrO3, R = Lu, Tb, Gd, Eu, Sm) crystallizing in the orthorhombic structure has been studied using Raman scattering and synchrotron powder x-ray diffraction up to 20 GPa. From our studies on RCrO3 we found that the octahedral tilts (distortions) increase with pressure. This is contrary to the earlier report which suggests that in LaCrO3, the distortions decrease with pressure leading to a more ordered phase at high pressure. Here, we observe that the rate of increase in distortion decreases with the increase in R-ion radii. This occurs due to the reduction in the compression of RO12 polyhedra with a corresponding increase in the compression of the CrO6 octahedra with increasing R-ion radii. From the Raman studies, we predict a critical R-ion radii, above which we expect the distortions in RCrO3 to reduce with increasing pressure leading to what is observed in the case of LaCrO3. These Raman results are consistent with our pressure dependent structural studies on RCrO3 (R = Gd, Eu, Sm). Also, our results suggest that the pressure dependence of Neel temperature, T NCr, (where the Cr3+ spin orders) in RCrO3 is mostly affected by the compressions of Cr-O bonds rather than the alteration of octahedral tilts.

Field effect transistors and photodetectors based on nanocrystalline graphene derived from electron beam induced carbonaceous patterns

We describe a transfer-free method for the fabrication of nanocrystalline graphene (nc-graphene) on SiO(2) substrates directly from patterned carbonaceous deposits. The deposits were produced from the residual hydrocarbons present in the vacuum chamber without any external source by using an electron beam induced carbonaceous deposition (EBICD) process. Thermal treatment under vacuum conditions in the presence of Ni catalyst transformed the EBIC deposit into nc-graphene patterns, confirmed using Raman and TEM analysis. The nc-graphene patterns have been employed as an active p-type channel material in a field effect transistor (FET) which showed a hole mobility of ~90 cm(2) V(-1) s(-1). The nc-graphene also proved to be suitable material for IR detection.

Superionic Phase Transition in KHSO4: A Temperature-Dependent Raman Investigation

Temperature-dependent Raman spectroscopic studies have been carried out on KHSO4 single crystals in the temperature range 298-493 K. A structural phase transition driven by the lattice and molecular disorder is observed at 473 K. The spectral data enable an understanding of the nature of the lattice disorder across the phase transition leading to the superionic phase. The disorder in the HSO4- polymeric hydrogen-bonded chain leading to a higher symmetry in the high temperature phase is clearly captured from our Raman results. The internal S-OH and S−O stretching modes and, to a limited extent, the external modes throw light on the disorder mechanism and the enhancement of conductivity after transition.

Octahedral distortion induced magnetic anomalies in LaMn0.5Co0.5O3 single crystals

Single crystals of LaMn0.5Co0.5O3 belonging to the ferromagnetic-insulator and distorted perovskite class were grown using a four-mirror optical float zone furnace. The as-grown crystal crystallizes into an orthorhombic Pbnm structure. The spatially resolved 2D Raman scan reveals a strain-induced distribution of transition metal (TM)–oxygen (O) octahedral deformation in the as-grown crystal. A rigorous annealing process releases the strain, thereby generating homogeneous octahedral distortion. The octahedra tilt by reducing the bond angle TM-O-TM, resulting in a decline of the exchange energy in the annealed crystal. The critical behavior is investigated from the bulk magnetization. It is found that the ground state magnetic behavior assigned to the strain-free LaMn0.5Co0.5O3 crystal is of the 3D Heisenberg kind. Strain induces mean field-like interaction in some sites, and consequently, the critical exponents deviate from the 3D Heisenberg class in the as-grown crystal. The temperature-dependent Raman sc...