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 N\'eel temperature, TNCr, (where the Cr3+ spin orders) in RCrO3 is mostly affected by the compressions of Cr-O bonds rather than the alteration of octahedral tilts.Comment: 17 pages, 8 figures This manuscript has been published in Material Research Expres

Spin-phonon coupling in multiferroic RCrO3_3 (R-Y, Lu, Gd, Eu, Sm): A Raman study

Raman study on a select few orthochromites, RCrO$_3$ (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 CrO$_6$ 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 important role in inducing switchable electric polarization.Comment: 6 pages (two column format), 7 figures; The updated version of the manuscript can be found at Euro. Phys. Lett. 101, 17008 (2013

Influence of lattice distortion on the Curie temperature and spin-phonon coupling in LaMn0.5_{0.5}Co0.5_{0.5}O3_{3}

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 $\textit{T}_{c}$ 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 $\textit{T}_{c}$. Raman scattering suggests the presence of spin-phonon coupling for both the phases around the $\textit{T}_{c}$. Electrical transport properties of both the phases have been investigated based on the lattice distortion.Comment: 9 figure

Raman and X-ray investigations of ferroelectric phase transition in NH₄HSO₄

Temperature-dependent Raman spectroscopy and X-ray diffraction studies have been carried out on NH₄HSO₄ single crystals in the temperature range 77–298 K. Two structural transitions driven by the molecular ordering and change in crystal symmetries are observed below 263 and 143 K. These phase transitions are marked by the anomalies in the temperature dependence of wavenumber and fwhm of several internal vibrational modes. The Raman spectra and X-ray data enable us to understand the nature of the molecular ordering resulting in the ferroelectric phase below 263 K, sandwiched between two nonferroelectric phases. The crystal structure of the ferroelectric phase is determined correctly as Pc, which has been earlier solved in Ba symmetry. The temperature dependent Raman and X-ray results suggest that the disorder to order transition leading to lower symmetry below 263 K is driven by the change in HSO₄^– ions and that below 143 K is driven by the change in both HSO₄^– and NH₄⁺ ions

Stress states in individual Si particles of a cast Al-Si alloy: Micro-Raman analysis and microstructure based modeling

The stress states in Si particles of cast Al-Si based alloys depend on its morphology and the heat treatment given to the alloy. The Si particles fracture less on modification and fracture more in the heat treated condition. An attempt has been made in this work to study the effect of heat treatment and Si modification on the stress states of the particles. Such understanding will be valuable for predicting the ductility of the alloy. The stress states of Si particles are estimated by Raman technique and compared with the microstructure-based FEM simulations. Combination of Electron Back-Scattered Diffraction (EBSD) and frequency shift, polarized micro-Raman technique is applied to determine the stress states in Si particles with (111) orientations. Stress states are measured in the as-received state and under uniaxial compression. The residual stress, the stress in the elastic-plastic regime and the stress which causes fracture of the particles is estimated by Raman technique. FEM study demonstrates that the stress distribution is uniform in modified Si, whereas the unmodified Si shows higher and more complex stress states. The onset of plastic flow is observed at sharp corners of the particles and is followed by localization of strain between particles. Clustering of particles generates more inhomogeneous plastic strain in the matrix. Particle stress estimated by Raman technique is in agreement with FEM calculations. (C) 2014 Elsevier B.V. All rights reserved

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 (Nc), trans (Nt) and zwitterion (Z*)] have been interpreted by Mulliken charge, Natural Bond Orbital (NBO) analysis and polarization versus electric field (P-E loop) studies. 1H and 13C 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 (ESIraPT and ESIerPT). Increased electrical conductivity (σac) with temperature and increased ferroelectric polarization at higher field verifies proton conduction in I7C

Brillouin Scattering Investigation of Solvation Dynamics in Succinonitrile-Lithium Salt Plastic Crystalline Electrolytes

Temperature dependent Brillouin scattering studies have been performed to ascertain the influence of solvent dynamics on ion-transport in succinonitrile-lithium salt plastic crystalline electrolytes. Though very rarely employed, we observe that Brillouin spectroscopy is an invaluable tool for investigation of solvent dynamics. Analysis of various acoustic (long wavelength) phonon modes observed in the Brillouin scattering spectra reveal the influence of trans-gauche isomerism and as well as ion-association effects on ion transport. Although pristine SN and dilute SN-LiClO(4) samples show only the bulk longitudinal-acoustic (LA) mode, concentrated SN-LiClO(4) (similar to 0.3-1 M) electrolytes display both the bulk LA mode as well as salt induced brillouin modes at ambient temperature. The appearance of more than one brillouin mode is attributed to the scattering of light from regions with different compressibilities (''compactness''). Correspondingly, these modes show a large decrease in the full width at half-maximum (abbreviated as nu(f)) as the temperature decreases. Anomalous temperature dependent behavior of nu(f) with addition of salt could be attributed to the presence of disorder or strong coupling with a neighbor. The shape of the spectrum was evaluated using a Lorentzian and Fano line shape function depending on the nature and behavior of the Brillouin modes

Few layer graphene to graphitic films: infrared photoconductive versus bolometric response

We report a comparative study of the performance of infrared (IR) photoconductive and bolometric detectors fabricated from few layer graphene (FLG) to graphitic films obtained by different methods. FLG films grown directly on insulating substrates with the aid of residual hydrocarbons and polymethylmethacrylate (PMMA) carbon sources show an IR photoresponse of 73% which is far higher compared to the FLG films (6–14%) obtained by CVD and Scotch tape methods. The photoconductive nature of FLG films is due to generation of photoexcited charge carriers. On the other hand, the photoresponse of the bulk graphitic films is bolometric in nature where the resistance changes are due to thermal effects. The IR photoresponse from these graphitic films is correlated with the Raman peak intensities which are very sensitive to the nature of the FLG

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 SiO₂ 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 cm² V^-1 s^-1. The nc-graphene also proved to be suitable material for IR detection

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 scattering study reveals strong spin-phonon coupling and the existence of two magnetic ground states in the same crystal. (C) 2014 AIP Publishing LLC