Emergence of the sub‐THz central peak at phase transitions in artificial BaTiO3/(Ba,Sr)TiO3 superlattices

A prominent central peak in the sub‐THz frequency range was observed in the Raman spectra of BaTiO₃/(Ba,Sr)TiO₃ (BT/BST) superlattice grown on (001)MgO substrate. Both soft and central mode show an anomaly around 200 K and 280 K, which can be correlated with orthorhombic to monoclinic phase transition of BST and BT, respectively. The observed temperature dependence of the central mode enabled us to explain rather broad temperature dependence of the dielectric permittivity previously observed in BT/BST superlattices. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Energy structure and absorption spectra of colloidal CdS nanocrystals in gelatin matrix

We investigate the energy structure of colloidal CdS nanocrystals by measuring the UV–vis absorption spectra. Nanocrystals were synthesized by sol–gel method in a gelatin matrix in the size range from 2.5 to 3.9 (±0.2) nm. In order to interpret the UV–vis absorption spectra we calculate the energy spectrum of electron quasi-stationary states using the model of open nanocrystal as well as the hole stationary spectrum in a two-band approach. It is shown that the main contribution to the absorption spectrum is made by interband transitions 1S_3/2→1S_e and 1P_3/2→1P_e, and its shape is determined by the size distribution of nanoparticles. For this system the estimated values of the effective masses of the heavy hole and light hole are 1.44m₀ and 0.28m₀, respectively.     

Intense laser field effects on the electron Raman scattering in a strained InGaN/GaN quantum well

The differential cross-section for an intersubband electron Raman scattering process in a strained InGaN/GaN quantum well in the presence of an intense laser field is studied. In the effective-mass approximation, the electronic structure is calculated by taking into account the effects of spontaneous and piezoelectric polarization fields on the confinement potential. Effects of laser field strength, indium composition and the well width on the differential cross-section of the strained quantum well are investigated. Results show that the position and the magnitude of the peaks of emission spectra considerably depend on the laser field strength as well as structural parameters.     

Optical,electrical and magnetic properties of nanostructured Mn3O4 synthesized through a facile chemical route

Nanostructured Mn₃O₄ sample with an average crystallite size of ∼15 nm is synthesized via the reduction of potassium permanganate using hydrazine. The average particle size obtained from the Transmission Electron Microscopy analysis is in good agreement with the average crystallite size estimated from X-ray diffraction analysis. The presence of Mn⁴⁺ ions at the octahedral sites is inferred from the results of Raman, UV–visible absorption and X-ray photoelectron spectroscopy analyzes. DC electrical conductivity of the sample in the temperature range 313–423 K, is about five orders of magnitude larger than that reported for single crystalline Mn₃O₄ sample. The dominant conduction mechanism is identified to be of the polaronic hopping of holes between cations in the octahedral sites. The zero field cooled and field cooled magnetization of the sample is studied in the range 20–300 K. The Curie temperature for the sample is about 45 K, below which the sample is ferrimagnetic. A blocking temperature of 35 K is observed in the field cooled curve. It is observed that the sample shows hysteresis at temperatures below the Curie temperature with no saturation, even at an applied field (20 kOe). The presence of an ordered core and disordered surface of spin arrangements is observed from the magnetization studies. Above the Curie temperature, the sample shows linear dependence of magnetization on applied field with no hysteresis characteristic of paramagnetic phase.     

Effect of Fe-doping on the structural,morphological and optical properties of ZnO nanoparticles synthesized by solution combustion process

The effect of Fe-doping on the structural, morphological and optical properties of ZnO nanoparticles synthesized by simple solution combustion process are reported. The powder XRD pattern indicates that the Fe-doped ZnO samples exhibit primary and secondary phases. The primary phase indicates the hexagonal wurtzite structure with the average crystalline size of around 25–50 nm and the secondary phase is associated with the face centered cubic structure of magnetite iron oxide. The elemental composition of pure and Fe-doped samples are evaluvated by EDX. The results of FE-SEM and HR-TEM cleary show that particles morphology have changed with respect to the incorporation of doping agent and particles are in aggregating nature. The vibrational properties of the synthesized ZnO nanoparticles are investigated by Raman scattering technique and it exhibits that the influence of Fe-doping significantly modify the lattice vibrational characteristics in ZnO sites. The optical properties of the Fe-doped ZnO nanoparticles are carried out by UV–vis absorption and PL spectra. The results of PL spectra show the near-band edge related emission as well as strong blue emissions in the Fe-doped ZnO nanoparticles.     

Synthesis,spatial structure and spectral properties of pyrylo‐4 (thio) squaraines variously substituted in cyclobutene moiety

Synthetic routes have been developed to a number of (thio) squaraine dyes containing the residues of CH‐acids at the central cyclobutene ring. The electronic and spatial structure as well as the chemical conversions and optical behaviour of the compounds obtained have been studied both theoretically and by X‐ray diffraction analysis, ¹H NMR and electronic spectroscopy. As shown, the electronic nature and sterical characteristics of the central ring substituents give rise to some general conformational features and crystal packing regularities and also govern the spectral position of the first π–π^* absorption band. The structure–property relationships established in the study provide guidance for the purposeful design of deeply coloured (thio) squaraines. Copyright © 2015 John Wiley & Sons, Ltd.     

Conformational stability and vibrational study of phenylacetyl chloride

The Fourier transform infrared spectroscopy and Fourier transform Raman spectra of phenylacetyl chloride were recorded and analyzed in the range 3500–400 and 3500–200 cm^?1 at room temperature, respectively. In order to obtain the structural information and conformational stabilities, a potential energy surface scan for internal rotation was carried out at the B3LYP/6‐31G(d) level. The potential energy surface reveals that the title compound has two minimal conformers (A and B). The optimized geometries, structural parameters, stabilities, energies, thermodynamic parameters, vibrational wavenumbers, infrared intensities, and Raman activities for the two conformers (A and B) have been obtained by employing B3LYP and MP2 calculations with 6‐311++G (d, p) basis sets. The conformational energy difference between A and B is very small, indicating that the B conformer coexists with the A conformer. The detailed vibrational assignments of vibrational spectra of each conformer have been made on the basis of the potential energy distributions analysis. The highest occupied molecular orbital –lowest unoccupied molecular orbital energy gap and molecular electrostatic potential of the two conformers have been also calculated for comparison of their chemical activities. Copyright © 2015 John Wiley & Sons, Ltd.     

Large-scale plasmonic-SERS templates by successive growth steps

This work presents the fabrication of large-scale tunable-plasmonic surface-enhanced Raman scattering (SERS) templates and investigates their Raman enhancement. Substrates for SERS were prepared by deposition of gold nanoparticles on a glass slide followed by their growth. A plasmon shift was observed upon growing due to the formation of elongated nanoparticles and their mutual coupling. The changes in particle size, shape and interparticle distances were indicated by SEM measurements. Surface-enhanced Raman spectra of Nile blue A at a very low concentration on top of a blocking layer were measured. The overall Raman enhancement is correlated with the number of growth steps. For excitation at 532 nm four growth steps lead to maximum enhancement. Better overlap of excitation laser and the plasmon resonances upon growing increased the enhancement until four steps while further growing decreased the enhancement. At longer wavelengths excitation (633 and 785 nm) the enhancement further increased beyond the fourth growth step. This enhancement is caused by the plasmon excitation of narrower gap sizes. The proposed procedure for the SERS substrates is simple, allows covering large surface areas and plasmon band tuning from 530 nm to the near infrared in order to increase overall Raman enhancement.     

Fe doping induced enhancement in room temperature ferromagnetism and selective cytotoxicity of CeO2 nanoparticles

In the present study, structural, optical, magnetic properties as well as cytotoxicity of undoped and Fe doped Ceria (CeO₂) nanoparticles synthesized by simple soft chemical method have been reported. SEM and XRD results have shown that the synthesized samples are comprised of ultrafine spherical nanoparticles having single phase cubic fluorite structure of CeO₂. Raman spectroscopy results have depicted a red shift in F_2g mode with Fe doping which reveals enhancement in the oxygen vacancies. The optical band gap calculated from UV–visible absorption spectra has been found to vary unsystematically with Fe doping which is associated with the creation of impurity level and abundance in oxygen vacancies with Fe doping. The oxygen vacancies have introduced the room temperature ferromagnetism (RTFM) in undoped and Fe doped CeO₂ nanoparticles. The saturation magnetization (M_s) value of pristine CeO₂ nanoparticles has been found to be 0.00083 emu/g which is increased up to 0.0126 emu/g for 7% Fe doped nanoparticles. For cytotoxicity tests, the synthesized nanoparticles induced effects on Neuroblastoma cancer cells & HEK-293 healthy cells have been analyzed via CCK-8 analysis. It has been observed that the prepared undoped and Fe doped CeO₂ nanoparticles have nontoxic nature towards healthy cells while they are extremely toxic towards cancerous cells. Furthermore, the anticancer activity is found to enhance with Fe doping. The selective toxicity and enhancement in anticancer activity with Fe doping has observed to be strongly correlated with reactive oxygen species (ROS) generation.