Raman scattering studies of individual polar semiconducting nanowires: phonon splitting and antenna effects

Results from Raman scattering experiments on individual crystalline GaP nanowires are presented which indicate that the shape of the nanowire, i.e., the high aspect ratio, may be responsible for two new phenomena involving optical phonons: (1) a shape-inducedsplitting of both the longitudinal optical (LO) and transverse optical (TO) phonons at the center of the Brillouin zone (q=0), and (2) a Raman scattering “antenna” effect which masks the normal Raman polarization selection rules. We suggest that (1) stems from the asymmetry in the long range dipolar sums that control the electromagnetic LO-TOsplitting, and we identify the Raman antenna effect (2) with the internal electric field created by Mie resonances in the nanowire driven by the incident laser field. Although these effects are reported here for GaP, they are expected to be general effects observable in many semiconducting nanowire systems. PACS 78.67.-n; 78.67.Lt; 78.30.-j; 78.30.Fs; 72.10.Di     

Raman spectrum of Si nanowires: temperature and phonon confinement effects

The Raman spectrum of Si nanowires (NWs) is a matter of controversy. Usually, the one-phonon band appears broadened and shifted. This behaviour is interpreted in terms of phonon confinement; however, similar effects are observed for NWs with dimensions for which phonon confinement does not play any relevant role. In this context, the temperature increase induced by the laser beam is recognized to play a capital role in the shape of the spectrum. The analysis of the Raman spectrum, under the influence of the heating induced by the laser beam, is strongly dependent on the excitation conditions and the properties of the NWs. We present herein an analysis of the Raman spectrum of Si NWs based on a study of the interaction between the laser beam and the NWs, for both ensembles of NWs and individual NWs, taking account of the temperature increase in the NWs under the focused laser beam and the dimensions of the NWs.     

Raman scattering from surface optical phonon mode in gallium phosphide nanomaterials

The Raman scattering from gallium phosphide (GaP) nanoparticles (~53 nm) and nanosolids has been investigated. By means of Lorentzian fitting of the Raman scattering spectra, a surface optical phonon (SO) peak located between the transverse optical (TO) phonon and longitudinal optical (LO) phonon frequencies became observable. It has been proved by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) that a core-shell heterostructure is characteristic of the structure of GaP nanoparticles. According to electromagnetic theory, the SO frequency of the piezoelectric/semiconductor heterostructural nanomaterials was calculated.     

Raman scattering from the upper and lower modes of surface phonon polaritons in ZnTe

The upper and lower modes of surface phonon polaritons have been observed in free-standing thin slabs (～7 μm) of single-crystal ZnTe by a conventional Raman-scattering technique at room temperature. The experimental dispersion relations were measured in various scattering angles (outside the sample) from 0.9° to 2.0° and agree with the theoretical dispersion relations. The main factors enabling us to observe the two surface modes are the appropriate selections of the material with a small attenuation factor for surface phonon polaritons and of the thickness of the sample slabs.     

Dispersive phonon modes by resonant Raman scattering in AgBr

Dispersive Raman modes are observed in AgBr at low temperatures when the incident laser light is tuned across the indirect Γ-L^′₃ exciton absorption. These modes occur as sidebands of the resonantly enhanced 2 TO(L), TO+LA(L) and 2 LA(L) Raman peaks and are interpreted as being due to three- and four-phonon processes, respectively. They involve longitudinal acoustic phonons near the Brillouin zone center that exhibit strong dispersion. From analysing the spectra the relaxation of the intermediate exciton state can be studied in detail. The model applied enables us to obtain directly the average effective mass of the ls indirect exciton as 1.5 electron masses.     

Raman scattering from plasmon-LO phonon coupled modes in ZnTe

Raman scattering spectra of LO phonon-plasmon coupled modes were observed at various temperatures below 400 K. The contributions of plasmon damping and phonon damping were analyzed by the use of the theoretical expression of the cross section and of Hall data. The temperature dependence of the calculated LO-phonon damping was discussed.     

Raman spectroscopy for study of interplay between phonon confinement and Fano effect in silicon nanowires

A combined effect of doping (type and species) and size on Raman scattering from silicon (Si) nanowires (NWs) has been presented here to study interplay between quantum confinement and Fano effects. The SiNWs prepared from low doping Si wafers show only confinement effect, as evident from the asymmetry in the Raman line‐shape, irrespective of the doping type. On the other hand SiNWs prepared from wafer with high doping shows the presence of electron–phonon interaction in addition to the phonon confinement effect as revealed from the presence of asymmetry and antiresonence in the corresponding Raman spectra. This combined effect induces an extra asymmetry in the lower energy side of Raman peak for n‐type SiNWs whereas the asymmetry flips from lower energy side to the higher energy side of the Raman peak in p‐type SiNWs. Such an interplay can be represented by considering a general Fano‐Raman line‐shape equation to take care of the combined effect in SiNWs. Copyright © 2015 John Wiley & Sons, Ltd.     

Double resonance in Raman scattering on single phonon modes of GaSe

Resonance in the Raman cross section for one-phonon modes of GaSe at 80°K has been observed for both incident and scattered photon energies equal to the direct exciton energy. The Raman efficiency spectrum within the region of resonance is shown to fit well with the shape computed from existing theories.     

Interplay between phonon confinement effect and anharmonicity in silicon nanowires

Getting light out of silicon is a difficult task since the bulk silicon has an indirect energy electronic band gap structure. It is expected that this problem can be circumvented by silicon nanostructuring, since the quantum confinement effect may cause the increase of the silicon band gap and shift the photoluminescence into the visible energy range. The increase in resulting structural disorder also causes the phonon confinement effect, which can be analyzed with a Raman spectroscopy. The large phonon softening and broadening, observed in silicon nanowires, are compared with calculated spectra obtained by taking into account the anharmonicity, which is incorporated through the three and four phonon decay processes into Raman scattering cross-section. This analysis clearly shows that the strong shift and broadening of the Raman peak are dominated by the anharmonic effects originating from the laser heating, while confinement plays a secondary role.     

Detection of invisible phonon modes in individual defect-free carbon nanotubes by gradient-field Raman scattering

We provide an effective method to investigate the field gradient effect in nanoconfined plasmon-matter interaction.Aligned ultralong SWNTs without defects were grown on marked substrates, followed by assembling gold nanoparticle clusters around individual nanotubes. The Raman scattering behavior of a nanotube placed in an atomic scale nanogap between adjacent nanoparticles was studied. In addition to the expected plasmon-induced Raman enhancement up to 103,the defect-free D-mode of an individual SWNT induced by gradient field is found for the first time. When the light is confined at atomic scale, gradient field Raman scattering becomes significant and dipole-forbidden phonon modes can be activated by quadrupole Raman tensor variation, indicating breakdown of the Raman selection rules.     

Raman spectra of CdS nanocrystals in Nafion: longitudinal optical and confined acoustic phonon modes

Quantum confinement effects on the longitudinal optical and acoustic phonons in CdS nanocrystals in the strongly confined regime in the polymer matrix Nafion are studied using Raman spectroscopy. The LO-phonon modes show size-dependent asymmetric broadening though the broadening and asymmetry are less than those predicted by the phonon confinement models. Two types of confined acoustic modes corresponding to n=1, l=0 and n=1, l=2 spheroidal vibrations are observed. Softening of the spheroidal modes is observed in the strongly confined regime.     

Raman scattering by phonon polaritons in ZnS

The experimental difficulties in recording the phonon-polariton spectra of ZnS crystals are discussed. The measured polariton dispersion in cubic ZnS is presented and is found to be in good agreement with the calculated one.     

Improved model of optical phonon confinement in silicon nanocrystals

We develop a model for calculating the Raman scattering spectra from phonons confined in for silicon nanocrystals, which is based on the familiar approach taking into account the uncertainty in the quasi-momentum of phonons localized in the nanocrystals. The model is considerably improved by taking into account dispersion of phonons not only in the magnitude of the quasi-momentum, but also in its direction. A significant refinement of the model is also due to the fact that phonon dispersion is calculated using the widely approved Keating model instead of being approximated by empirical expressions as was done in earlier approaches. The calculations based on this model make it possible to determine the sizes of silicon nanocrystals more precisely from analysis of the experimental Raman spectra.     

Forward Raman scattering in GaAs/AlAs superlattices: Study of optical phonon anisotropy

We present the forward Raman scattering study of zone-centre optical phonon anisotropy in short-period GaAs/AlAs superlattices. Experiments were performed on specially prepared superlattice structures having anti-reflection dielectric coatings and removed substrates. The experimental data are compared with the angular dispersion of superlattice optical phonons calculated within the dielectric susceptibility model. We have found a good agreement between the experimental data and the calculations taking into account interface disorder. Received 9 September 1998 and Received in final form 22 October 1998     

One phonon resonant Raman scattering in a quantized spherical film

We have presented a theoretical calculation of the differential cross section (DCS) for the electron Raman scattering (ERS) process associated with surface optical (SO) phonon modes in a semiconductor quantized spherical film. We consider the Fröhlich electron–phonon interaction in the framework of the dielectric continuum approach. We study the selection rules for the processes. Singularities are found to be size-dependent and by varying the size of the QDs, it is possible to control the frequency shift in the Raman spectrum. A discussion of the phonon behavior for the films with large and small size is presented. The numerical results are also compared with that of experiments.     

Broad spectral photonic crystal fiber surface enhanced Raman scattering probe

A broad spectral surface enhanced Raman scattering sensor is developed using the solid core holey photonic crystal fiber with silver nanoparticles cluster. This SERS probe offers an operational excitation wavelength range overlaying visible light and near infrared light. The PCF SERS sensing is demonstrated in the detection of the 4-Mercaptobenzoic acid (10⁻⁶ M) solution with 514.5 and 785 nm excitation. In this structure of PCF sensor, the related analysis shows that leakage modes also make an important contribution in the SERS activity not only by the evanescent field way.     

Raman scattering by electron and phonon excitations in FeSi

The temperature evolution of Raman scattering by electron and phonon excitations in FeSi is studied within the range of 10–500 K. At low temperatures, the frequency dependence for the spectra of light scattered by electrons exhibits vanishing intensity in the range up to 500–600 cm^–1, which suggests the existence of an energy gap of about 70 meV. The calculations of the electronic excitation spectra based on the band structure determined using the LDA+DMFT technique (local electron density + dynamic mean field approximation) are in good agreement with the low-temperature experimental data and confirm that FeSi is a material with intermediate electron correlations. The changes in the shape of the electronic excitation spectrum and in the self-energy of optical phonons indicate a transition to the metallic state above 100 K. The analysis of experimental data demonstrates an appreciable decrease in the electron lifetime with the growth of temperature determining the (insulator–poor metal) transition.