Electronic states of trans-polyacetylene, poly(p-phenylene vinylene) and sp-hybridised carbon species in amorphous hydrogenated carbon probed by resonant Raman scattering

Inclusions of sp-hybridised, trans-polyacetylene [trans-(CH)x] and poly(p-phenylene vinylene) (PPV) chains are revealed using resonant Raman scattering (RRS) investigation of amorphous hydrogenated carbon (a-C:H) films in the near IR – UV range. The RRS spectra of trans-(CH)x core Ag modes and the PPV CC-H phenylene mode are found to transform and disperse as the laser excitation energy ћωL is increased from near IR through visible to UV, whereas sp-bonded inclusions only become evident in UV. This is attributed to ћωL probing of trans-(CH)x chain inhomogeneity and the distribution of chains with varying conjugation length; for PPV to the resonant probing of phelynene ring disorder; and for sp segments, to ћωL probing of a local band gap of end-terminated polyynes. The IR spectra analysis confirmed the presence of sp, trans-(CH)x and PPV inclusions. The obtained RRS results for a-C:H denote differentiation between the core Ag trans-(CH)x modes and the PPV phenylene mode. Furthermore, it was found that at various laser excitation energies the changes in Raman spectra features for trans-(CH)x segments included in an amorphous carbon matrix are the same as in bulk trans-polyacetylene. The latter finding can be used to facilitate identification of trans-(CH)x in the spectra of complex carbonaceous materials.

Layer-dependent resonant Raman scattering of a few layer MoS2

We report resonant Raman scattering of MoS2 layers comprising of single, bi, four and seven layers, showing a strong dependence on the layer thickness. Indirect band gap MoS2 in bulk becomes a direct band gap semiconductor in the monolayer form. New Raman modes are seen in the spectra of single- and few-layer MoS2 samples which are absent in the bulk. The Raman mode at similar to 230 cm(-1) appears for two, four and seven layers. This mode has been attributed to the longitudinal acoustic phonon branch at the M point (LA(M)) of the Brillouin zone. The mode at similar to 179 cm(-1) shows asymmetric character for a few-layer sample. The asymmetry is explained by the dispersion of the LA(M) branch along the G-M direction. The most intense spectral region near 455 cm(-1) shows a layer-dependent variation of peak positions and relative intensities. The high energy region between 510 and 645 cm(-1) is marked by the appearance of prominent new Raman bands, varying in intensity with layer numbers. Resonant Raman spectroscopy thus serves as a promising non invasive technique to accurately estimate the thickness of MoS2 layers down to a few atoms thick. Copyright (C) 2012 John Wiley & Sons, Ltd.

Polarization dependence of double resonant Raman scattering band in bilayer graphene

The polarization dependence of the double resonant Raman scattering (2D) band in bilayer graphene (BLG) is studied as a function of the excitation laser energy. It has been known that the complex shape of the 2D band of BLG can be decomposed into four Lorentzian peaks with different Raman frequency shifts attributable to four individual scattering paths in the energy-momentum space. From our polarization dependence study, however, we reveal that each of the four different peaks is actually doubly degenerate in its scattering channels, i.e., two different scattering paths with similar Raman frequency shifts for each peak. We find theoretically that one of these two paths, ignored for a long time, has a small contribution to their scattering intensities but are critical in understanding their polarization dependences. Because of this, the maximum-to-minimum intensity ratios of the four peaks show a strong dependence on the excitation energy, unlike the case of single-layer graphene (SLG). Our findings thus reveal another interesting aspect of electron-phonon interactions in graphitic systems. © 2014 Elsevier Ltd. All rights reserved.

Resonant Raman scattering of a-SiNx : H

Micro-Raman measurements were carried out to investigate the microstructure of amorphous silicon-nitrogen alloy (a-SiNx:H) samples with different N contents prepared by plasma enhanced chemical vapor deposition (PECVD). Resonant Raman effect was discovered by using 647.1- and 514.5-nm excitation wavelengths. The frequency of TO mode downshifts with increasing photon energy without varying its width, while LO mode expands to a great extent. The frequency-dependent shift of TO band is explained by heterogeneous structure model and quantum confinement model, and the width expansion of LO mode may be related to the overlapping of LA and LO bands. (C) 2001 Elsevier Science B.V. All rights reserved.

NEAR-RESONANT RAMAN-SCATTERING FROM GAAS/ALAS SUPERLATTICES

This article presents the results of near-resonant Raman scattering measurements on GaAs/AlAs superlattices at room temperature. A strong enhancement of GaAs LO phonon-even modes resulted owing to a dipole-allowed Frohlich interaction in superlattices. Similar to the previous results, the LO phonon-even modes in a polarized configuration are observed. In contrast to previous work, however, what we observed in depolarized configurations is the LO phonon-odd modes instead of even modes. It is confirmed that the selection rules for near-resonant Raman scattering from LO phonons in this kind of superlattices are the same as those for off-resonant scattering. From the second-order Raman scattering, it is confirmed that polarized second-order Raman scattering spectra consist of overtones and combinations of two even modes, and depolarized second-order Raman scattering spectra consist of combinations of an even mode and an odd mode. Our experimental results coincide with the predictions using the recently developed Huang-Zhu model. A brief discussion on interface modes and their combination with confined modes is also presented.

Resonant Raman Scattering and Photoluminescence Emissions from Above Bandgap Levels in Dilute GaAsN Alloy

The transitions of E0 ,E0 ＋A0, and E＋ in dilute GaAs（1-x） Nx alloys with x = 0.10% ,0.22% ,0.36% ,and 0.62% are observed by micro-photoluminescence. Resonant Raman scattering results further confirm that they are from the intrinsic emissions in the studied dilute GaAsN alloys rather than some localized exciton emissions in the GaAsN alloys. The results show that the nitrogen-induced E E＋ and E0 ＋ A0 transitions in GaAsN alloys intersect at a nitrogen content of about 0.16%. It is demonstrated that a small amount of isoelectronic doping combined with micro-photoluminescence allows direct observation of above band gap transitions that are not usually accessible in photoluminescence.

Surface-enhanced resonant Raman spectroscopy (SERRS) of single-walled carbon nanotubes absorbed on the Ag-coated anodic aluminum oxide (AAO) surface

In this paper, we developed a new kind of substrate, the silver-coated anodic aluminum oxide (AAO), to investigate the characters of surface-enhanced resonant Raman scattering (SERRS) of the dilute single-walled carbon nanotubes. Homogeneous Ag-coated AAO substrate was obtained by decomposing the AgNO3 on the surface of AAO. single-walled carbon nanotubes (SWNTs) were directly grown onto this substrate through floating catalyst chemical vapor deposition method (CVD). SERRS of SWNTs was carried out using several different wavelength lasers. The bands coming from metallic SWNTs were significantly enhanced. The two SERRS mechanisms, the "electromagnetic" and "chemical" mechanism, were mainly responsible for the experiment results. (c) 2005 Elsevier B.V. All rights reserved.

Observation of the resonant Raman behavior of individual single-walled carbon nanotubes

The different resonant Raman scattering process of single-walled carbon nanotubes (SWNTs) has been found between the Stokes and anti-Stokes sides of the radial breathing modes (RBMs), and this provides strong evidence that Raman spectra of some special diametric SWNTs are in resonance with their electronic transitions between the singularities in the one-dimensional electronic density of states in the valence and conduction bands, and other SWNTs axe beyond the resonant condition. Because of the coexistence of resonant and non-resonant Raman scattering processes for different diametric SWNTs, the relative intensity of each RBM does not reflect the proportion of a particular SWNT.

SURFACE-ENHANCED RAMAN SCATTERING: METAL NANOSTRUCTURES COATED WITH LANGMUIR-BLODGETT FILMS

This review deals with surface-enhancved Raman scattering (SERS) employing Langmuir-Blodgett (LB) films, which serve as model systems for developing theoretical and experimental studies to elucidate the SERS effect. In addition, LB films have be used as integral parts of molecular architectures for SERS-active substrates. On the other hand, SERS and surface-enhaced resonant Raman scattering (SERRS) have allowed various properties of LB films to be investigated, especially those associated with molecular-level interactions. In the paper, emphasis is placed on single molecule detection (SMD), where the target molecule is diluted on an LB matrix of spectral silent material (low Raman cross section). The perspectives and challenges for combining SERS and LB films are also discussed.

Surface-enhanced raman scattering: metal nanostructures coated with langmuir-blodgett films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Disordered matter studied by x-ray Raman scattering

Spectroscopy can provide valuable information on the structure of disordered matter beyond that which is available through e.g. x-ray and neutron diffraction. X-ray Raman scattering is a non-resonant element-sensitive process which allows bulk-sensitive measurements of core-excited spectra from light-element samples. In this thesis, x-ray Raman scattering is used to study the local structure of hydrogen-bonded liquids and solids, including liquid water, a series of linear and branched alcohols, and high-pressure ice phases. Connecting the spectral features to the local atomic-scale structure involves theoretical references, and in the case of hydrogen-bonded systems the interpretation of the spectra is currently actively debated. The systematic studies of the intra- and intermolecular effects in alcohols, non-hydrogen-bonded neighbors in high-pressure ices, and the effect of temperature in liquid water are used to demonstrate different aspects of the local structure that can influence the near-edge spectra. Additionally, the determination of the extended x-ray absorption fine structure is addressed in a momentum-transfer dependent study. This work demonstrates the potential of x-ray Raman scattering for unique studies of the local structure of a variety of disordered light-element systems.

Phonon-induced Raman scattering in GaNAs

The Raman scattering spectra of MBE-grown GaNAs epilayers were investigated. The resonant enhancement of Raman scattering due to the E+ states in the conduction band was observed and the Raman peaks related to the phonons at non-Gamma points of the Brillouin Zone were detected. II was clearly seen that the local vibrational mode induced by nitrogen impurities evolves to the GaN-like lattice phonon mode when the nitrogen content increases. By comparing the Raman spectra measured before and after 850 degreesC rapid thermal annealing, it was tentatively suggested that two weak peaks were induced by the pairing or clustering effect of nitrogen.

A RESONANT RAMAN-STUDY ON PHONONS IN GAINAS/ALINAS MULTIPLE-QUANTUM WELLS

The LO phonon modes in the barrier layers of a GaInAs/AlInAs multiple quantum well structure are investigated by resonance Raman scattering (RRS), the excitation laser photon energy tuned to resonate with the above barrier interband transition energy. The resonance enhancement of LO phonon peaks are shown to be caused by Frohlich electron-phonon interaction. The pressure-dependent profiles for both AlAs-like (LO(2) mode) and InAs-like (LO(1) mode) Raman peak intensities are well fitted by the Gaussian lineshape. The shift between these two profiles can be explained by the outgoing RRS mechanism, providing information on the pressure-induced shift of the excitonic transition energy. The amplitude ratios of the two profiles are close to 1, showing a well defined two-mode behavior and the nearly equal polarizability for Al-As and In-As bonds in AlInAs alloy.