Origin of visible photoluminescence from porous silicon as studied by Raman spectroscopy

In this paper we discuss the different models proposed to explain the visible luminescence in porous silicon (PS). We review our recent photoluminescence and Raman studies on PS as a function of different preparation conditions and isochronal thermal annealing. Our results can be explained by a hybrid model which incorporates both nanostructures for quantum confinement and silicon complexes (such as SiHx, and siloxene) and defects at Si/SiO2, interfaces as luminescent centres.

Structural Hypotheses And Raman-Spectroscopy Investigations Of Glasses Belonging To The B2s3-Li2s-Lii System

A previous B-11 nuclear magnetic resonance investigation of glasses belonging to the B2S3-Li2S-LiI system had allowed the authors to determine the variation of the number of three and four coordinated boron atoms with composition. These results, in addition to the observation that vitreous B2S3 quite easily forms fibres during casting, have led us to propose structural hypotheses for B2S3 based glasses, which are supported by the present Raman spectroscopy study. For vitreous B2S3 the spectra were accounted for on the basis of the various types of BS3/2 triangles proposed by the model. Molecular orbital considerations allowed us to assign the most significant lines for the binary glasses by assuming that BS3/2 triangles (with or without nonbridging sulphur atoms) and BS4 tetrahedra were present. In the ternary system, lithium iodide has been found to interact slightly on the structural entities, altering their vibrational characteristics without fundamentally modifying their nature.

Raman Spectroscopy of the Charge Transfer Complex (TTF)x C60 Br8

We report Raman studies on powder samples of the charge transfer complex (TTF)(x)C60Br8 at room temperature. The phonons show considerable softening with respect to the frequencies observed in the Raman spectrum of solid C60Br8. The strongest mode at 1464 cm(-1) in C60Br8 is red shifted to a doublet with peaks at 1414 and 1421 cm(-1), implying an average phonon softening Delta omega of -47 cm(-1). A comparison with the phonon softening of the corresponding A(g)(2) mode in alkali-doped C-60 (Delta omega similar to -36 cm(-1) for A(6)C(60), A = K, Rb or Cs) suggests that 8 electrons are transferred per C60Br8 molecule in the charge transfer complex. The mode at 503 cm(-1) in C60Br8 is shifted upwards, similar to that in A(6)C(60) compounds.

A determination of the structure of the intramolecular charge transfer state of 4-dimethylaminobenzonitrile (DMABN) by time-resolved resonance Raman spectroscopy

Picosecond time-resolved resonance Raman spectra of the A (intramolecular charge transfer, ICT) state of DMABN, DMABN-d(6) and DMABN-N-15 have been obtained. The isotopic shifts identify the nu (s)(ph-N) mode as a band at 1281 cm(-1). The similar to 96 cm(-1) downshift of this mode from its ground state frequency rules out the electronic coupling PICT model and unequivocally supports the electronic decoupling TICT model. However, our results suggest some pyramidal character of the A state amino conformation.

Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single ``do-it-all'' technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-mu s) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy.

Realization of thermally durable close-packed 2D gold nanoparticle arrays using self-assembly and plasma etching

Realization of thermally and chemically durable, ordered gold nanostructures using bottom-up self-assembly techniques are essential for applications in a wide range of areas including catalysis, energy generation, and sensing. Herein, we describe a modular process for realizing uniform arrays of gold nanoparticles, with interparticle spacings of 2 nm and above, by using RF plasma etching to remove ligands from self-assembled arrays of ligand-coated gold nanoparticles. Both nanoscale imaging and macroscale spectroscopic characterization techniques were used to determine the optimal conditions for plasma etching, namely RF power, operating pressure, duration of treatment, and type of gas. We then studied the effect of nanoparticle size, interparticle spacing, and type of substrate on the thermal durability of plasma-treated and untreated nanoparticle arrays. Plasma-treated arrays showed enhanced chemical and thermal durability, on account of the removal of ligands. To illustrate the application potential of the developed process, robust SERS (surface-enhanced Raman scattering) substrates were formed using plasma-treated arrays of silver-coated gold nanoparticles that had a silicon wafer or photopaper as the underlying support. The measured value of the average SERS enhancement factor (2 x 10(5)) was quantitatively reproducible on both silicon and paper substrates. The silicon substrates gave quantitatively reproducible results even after thermal annealing. The paper-based SERS substrate was also used to swab and detect probe molecules deposited on a solid surface.

Study of the effect of alkali mixture on V-O bond length in Oxyfluoro Vanadate glasses using Raman spectroscopy

Raman spectroscopic study on Oxyfluoro Vanadate glasses containing various proportions of lithium fluoride and rubidium fluoride was carried out to see an effect of mixture of alkali on vanadium-oxygen (V-O) bond length. Glasses with a general formula 40V(2)O(5) - 30BaF(2) - (30 - x) LiF - xRbF (x = 0-30) were prepared. Room temperature Raman spectra of these glass samples were recorded in back scattering geometry. The data presented is in ``reduced Raman intensity'' form with maximum peak scaled to 100. We have used v = Aexp(BR), where A and B are fitting parameters, to correlate the bond length R with Raman scattering frequency v. We observed that variation in bond length and its distribution about a most probable value can be correlated to the alkali environment present in these glasses. We also observed that all rubidium environment around the network forming unit is more homogenous than all lithium environment.

Probing disorder and transport properties in polypyrrole thin-film devices by impedance and Raman spectroscopy

In the present study, impedance and Raman spectroscopy are adopted to probe the nature and extent of disorder to correlate with transport properties in doped polypyrrole (PPy) thin-film devices, synthesized electrochemically at different temperatures. A comparative study of the impedance spectroscopy is performed on PPy devices by both experimental and simulation approach with varying extent of disorder. The impedance measurements of PPy devices are well described by introducing a constant phase element (CPE) (Q) in modified RQ circuit, which accounts for frequency dependence of dielectric response. However, for the PPy grown at lower temperature, an equivalent circuit consisting of two such RQ elements in series is used for successful modelling of the impedance results, which accounts for the depletion region near the electrode. Raman spectroscopy and the de-convoluted spectra are successfully studied to probe the variation in C=C bond stretching and distribution of conjugation length, which relates to disorder in PPy films and the interpretation is well correlated to the impedance results.

Classification of Myopathies on Molecular basis in Drosophila using Raman spectroscopy

Myopathies are muscular diseases in which muscle fibers degenerate due to many factors such as nutrient deficiency, infection and mutations in myofibrillar etc. The objective of this study is to identify the bio-markers to distinguish various muscle mutants in Drosophila (fruit fly) using Raman Spectroscopy. Principal Components based Linear Discriminant Analysis (PC-LDA) classification model yielding >95% accuracy was developed to classify such different mutants representing various myopathies according to their physiopathology.

Classification of Myopathies on Molecular basis in Drosophila using Raman spectroscopy

Myopathies are muscular diseases in which muscle fibers degenerate due to many factors such as nutrient deficiency, infection and mutations in myofibrillar etc. The objective of this study is to identify the bio-markers to distinguish various muscle mutants in Drosophila (fruit fly) using Raman Spectroscopy. Principal Components based Linear Discriminant Analysis (PC-LDA) classification model yielding >95% accuracy was developed to classify such different mutants representing various myopathies according to their physiopathology.

Total internal reflection Raman spectroscopy of poly(alpha-olefin) oils in a lubricated contact

The rheology of a poly(alpha-olefin) base oil (PAO) in a sliding point contact has been investigated by total internal reflection (TIR) Raman spectroscopy. TIR Raman has the sensitivity to analyse nanometer-thick lubricant films in a tribological contact. The Raman signal generated from the sliding contact was used to determine the lubricant film thickness. The experimentally obtained film thicknesses were compared with theoretical calculations and a transition from Newtonian to non-Newtonian behaviour was observed at high shear rates. The Raman spectra showed no significant changes in the conformation of the PAO chains under the applied conditions of pressure and shear, but the polarisation dependence of the spectra revealed a preferred orientation of the hydrocarbon side chains in the shear-thinned region. Monolayers formed by a boundary lubricant, arachidic acid, dissolved in the PAO could be detected on the surfaces in the elastohydrodynamic regime.

Study Of Lattice Dynamics In Yttrium Doped NdMnO3 Using Raman Spectroscopy

A systematic study of Raman spectra on Yttrium doped NdMnO3 polycrystalline samples was undertaken to understand the lattice dynamics in this compound. Raman active phonons were analyzed and the observed peak were assigned to elucidate various phonon modes in the range (200 - 800) cm(-1). It was observed that at 325 cm(-1) phonon frequency shifts upward as much as upto 4 % with increase in Yttrium content. Lattice distortions manifest themselves by frequency shifts in both bending and tilt modes of MnO6 octahedra, resulting in increase of Raman band line-widths.

Light Induced Metastable State of Silver Nitroprusside Probed by Raman Spectroscopy

Low temperature Raman spectroscopic measurements on silver nitroprusside (AgNP), Ag-2Fe(CN)(5)NO] powders display reversible features of a partially converted metastable state. The results are compared with similarly observed metastable state in case of sodium nitroprusside (NaNP) and the differences have been discussed in terms of possible resistance to metastable state formation offered by silver atoms on the basis of hard soft acid base (HSAB) theory.