Low frequency Raman scattering of anatase titanium dioxide nanocrystals

TiO₂ nanoparticle of size 7.8 nm are synthesized by wet chemical route and characterized by low-frequency Raman scattering (LFRS), transmission electron microscopy (TEM) and X-ray diffraction. The low frequency peaks in the Raman spectra have been explained using the Lamb's theory that predicts the vibrational frequencies of a homogeneous elastic body of spherical shape. Our results show that the observed low-frequency Raman scattering originates from the spherical (l=0) and quadrupolar vibrations (l=2) of the spheriodal mode due to the confinement of acoustic vibrations in TiO₂ nanoparticles. In addition to the low-frequency peak due to the vibrational quadrupolar and spheriodal modes, a band is also observed, which is assigned to the Raman forbidden torsional l=2 mode originating from the near spherical shape of the TiO₂ nanoparticles. The size distribution is also obtained from LFRS, which is in good agreement with TEM.     

Zn/ZnO纳米颗粒的表面声子Raman散射

Ｚｎ／ＺｎＯ纳米颗粒的表面声子Ｒａｍａｎ散射许建峰黄亚彬莫育俊（河南大学物理系开封４７５００１）ＲａｍａｎＳｃａｔｅｒｉｎｇｆｒｏｍＳｕｒｆａｃｅＰｈｏｎｏｎｓｉｎＺｎ／ＺｎＯＮａｎｏｐａｒｔｉｃｌｅｓＸｕＪｉａｎｆｅｎｇ，ＨｕａｎｇＹａｂｉｎ，Ｍｏ...     

Theory of Raman light scattering by nanocrystal acoustic vibrations

A theory of Raman scattering of light by acoustic phonons in spherical nanocrystals of zinc-blende and wurtzite semiconductors has been developed with the inclusion of the complex structure of the valence band. The deformation-potential approximation was used to describe the exciton-phonon interaction. It is shown that this approximation allows only Raman scattering processes involving spheroidal acoustic phonons with a total angular momentum F=0 or 2. The effect of phonon quantum confinement on linewidth in Raman scattering spectra and scattered polarization is analyzed. An expression for the shape of the spectral line corresponding to nonresonant scattering from F=0 phonons was obtained. Fiz. Tverd. Tela (St. Petersburg) 41, 1473–1483 (August 1999)     

Low-frequency Raman scattering from CeO<Subscript>2</Subscript> nanoparticles

Raman scattering measurements were performed on CeO₂ nanoparticles at room temperature. Low-frequency modes are assigned to confined acoustic vibrations of spherical CeO₂ nanoparticles. Frequencies of these vibrational modes have been calculated in the elastic continuum approximation, which considers a nanoparticle as a homogeneous elastic sphere. We assumed stress-free boundary conditions. The specific dependence of the vibrational frequency on the particle diameter enables the determination of the particle size from the experimental Raman frequency. The particle size value calculated in this way agrees well with the value acquired from the phonon confinement model. PACS 61.46.Df; 73.63.Bd; 63.22.+m     

Stimulated Low-Frequency Raman Scattering in LaF<Subscript>3</Subscript> Suspensions

We observe stimulated low-frequency Raman scattering (SLFRS) caused by laser pulse interaction with acoustic vibrations of nanoparticles in water suspensions of LaF₃ nanoparticles. We show that frequency shifts of the scattering correspond to the eigenfrequencies of nanoparticles vibrations. LaF₃ nanoparticles were synthesized in the presence of glycine by a double jet precipitation technique at various initial concentrations of reagents. We investigate the morphologies and particle sizes as well as size distributions of the particles prepared using transmission electron microscopy (TEM) and dynamical light scattering (DLS). In view of the absorption spectroscopy, we show that the reaction system components and products have no absorption in the visible region, including λ = 694.3 nm. From the luminescence spectroscopy, we find also that they do not emit at λ = 694.3 nm excitation.     

Surface-enhanced Raman spectroscopy of semiconductor nanostructures

We review our recent results concerning surface-enhanced Raman scattering (SERS) by confined optical and surface optical phonons in semiconductor nanostructures including CdS, CuS, GaN, and ZnO nanocrystals, GaN and ZnO nanorods, and AlN nanowires. Enhancement of Raman scattering by confined optical phonons as well as appearance of new Raman modes with the frequencies different from those in ZnO bulk attributed to surface optical modes is observed in a series of nanostructures having different morphology located in the vicinity of metal nanoclusters (Ag, Au, and Pt). Assignment of surface optical modes is based on calculations performed in the frame of the dielectric continuum model. It is established that SERS by phonons has a resonant character. A maximal enhancement by optical phonons as high as 730 is achieved for CdS nanocrystals in double resonant conditions at the coincidence of laser energy with that of electronic transitions in semiconductor nanocrystals and localized surface plasmon resonance in metal nanoclusters. Even a higher enhancement is observed for SERS by surface optical modes in ZnO nanocrystals (above 10⁴). Surface enhanced Raman scattering is used for studying phonon spectrum in nanocrystal ensembles with an ultra-low areal density on metal plasmonic nanostructures.     

Raman scattering of Ge dot superlattices

Self-organised Ge dot superlattices grown by molecular beam epitaxy of Ge and Si layers utilizing Stranski-Krastanov growth mode were investigated by Raman spectroscopy. An average size of Ge quantum dots was obtained from transmission electron microscopy measurements. The strain and interdiffusion of Ge and Si atoms in Ge quantum dots were estimated from the analysis of frequency positions of optical phonons observed in the Raman spectra. Raman scattering by folded longitudinal acoustic phonons in the Ge dot superlattices was observed and explained using of elastic continuum theory. Received 25 January 2000     

Acoustic phonons transport in a quantum waveguide embedded double defects

By using scattering matrix method, we investigate the acoustic phonons transport in a quantum waveguide embedded double defects at low temperatures. When acoustic phonons propagate through the waveguide, the total transmission coefficient versus the reduced phonon frequency exhibits a series of resonant peaks and dips, and acoustic waves interfere with each other in the waveguide to form standing wave with particular wavelengths. In the waveguide with void defects, acoustic phonons whose frequencies approach zero can transport without scattering. The acoustic phonons propagating in the waveguide with clamped material defects, the phonons frequencies must be larger than a threshold frequency. It is also found that the thermal conductance versus temperature is qualitatively different for different types of defects. At low temperatures, when the double defects are void, the universal quantum thermal conductance and a thermal conductance plateau can be clearly observed. However, when the double defects consist of clamped material, the quantized thermal conductance disappears but a threshold temperature where mode 0 can be excited emerges. The results can provide some references in controlling thermal conductance artificially and the design of phonon devices.     

Resonant Raman scattering in nanostructures with InGaAs/AlAs quantum dots

Raman scattering by optical phonons in In_xGa_{1 ? x} As/AlAs nanostructures with quantum dots has been studied experimentally for compositions corresponding to x = 0.3?1 under out-resonance conditions. Features due to scattering by GaAs-and InAs-like optical phonons in quantum dots have been detected, and the phonon frequencies have been determined as a function of the dot composition. With increasing excitation energy, a red shift is observed in the frequency of the GaAs-like phonon in quantum dots, which testifies to Raman scattering selective by the size of quantum dots. Under resonant conditions, multiphonon light scattering by optical and interface phonons is observed up to the third order, including overtones of the first-order phonons of InGaAs and AlAs materials and their combinations.     

Acoustic phonons transport in a quantum waveguide embedded double defects

By using scattering matrix method, we investigate the acoustic phonons transport in a quantum waveguide embedded double defects at low temperatures. When acoustic phonons propagate through the waveguide, the total transmission coefficient versus the reduced phonon frequency exhibits a series of resonant peaks and dips, and acoustic waves interfere with each other in the waveguide to form standing wave with particular wavelengths. In the waveguide with void defects, acoustic phonons whose frequencies approach zero can transport without scattering. The acoustic phonons propagating in the waveguide with clamped material defects, the phonons frequencies must be larger than a threshold frequency. It is also found that the thermal conductance versus temperature is qualitatively different for different types of defects. At low temperatures, when the double defects are void, the universal quantum thermal conductance and a thermal conductance plateau can be clearly observed. However, when the double defects consist of clamped material, the quantized thermal conductance disappears but a threshold temperature where mode 0 can be excited emerges. The results can provide some references in controlling thermal conductance artificially and the design of phonon devices.     

Folded acoustic phonons in Si/Ge superlattices with Ge quantum dots

The spectra of Raman scattering by folded acoustic phonons in Si/Ge superlattices with pseudomorphic layers of Ge quantum dots (QDs) grown by low-temperature (T = 250°C) molecular beam epitaxy are studied. New features of the folded phonon lines related to the resonant enhancement and unusual intensity ratio of the doublet lines that cannot be explained by the existing theory have been observed. The observed modes are shown to be related to the vibrations localized to the QDs and induced by the folded phonons of the Si spacer layers. The calculations performed in the model of a one-dimensional chain of atoms have allowed the nature of the localization of acoustic phonons attributable to a modification of the phonon spectrum of a thin QD layer to be explained. The observed intensity ratio of the folded phonon doublet lines is caused by asymmetry of the relief of the QD layers.     

RAMAN SCATTERING INTENSITIES OF FOLDED LONGITUDINAL ACOUSTIC PHONONS IN GexSi1-x/Si SUPERLATTICES

In terms of photoelastic mechanism we have investigated the Raman scattering intensities of the folded longitudinal acoustic (FLA) phonons in Ge_xSi_1-x/ Si superlattices (SLs), taking into account the differences between the acoustic and photoelastic parameters of the two constituents in the SLs. The relative intensities calculated for the FLA phonons are in excellent agreement with the experimental results at the frequencies up to about 50 cm^-1. The broadening of the linewidth arising from the so called strong acoustic attenuation, which was reported previously located around the frequency 15 cm^-1 in Ge_xSi_1-x/Si SLs(x≈0.5), has not been observed in this work.     

Influence of the degree of disorder of amorphous solids on the intensity of light scattering by acoustic phonons

It is observed experimentally that in the low-frequency Raman light scattering spectrum of amorphous porous silicon the boson peak situated in the acoustic range is more sensitive to the structural order than the optical mode presently used to determine the degree of disorder. It is shown that this is because, unlike the coefficient of interaction with optical vibrations, the coefficient of interaction between light and acoustic vibrations contains an additional factor, the square of the reciprocal correlation length of the vibrational excitations, i.e., the intensity of light scattering by acoustic phonons has an additional dependence on the degree of disorder. Zh. éksp. Teor. Fiz. 114, 315–321 (July 1998)     

Coherent Excitation of Sodium Chloride Nanoparticles

We register stimulated low-frequency Raman scattering (SLFRS) caused by laser-pulse interaction with nanoparticle acoustic vibrations in an ethanol suspension of sodium chloride nanoparticles and measure the SLFRS conversion efficiency and threshold. Frequency shifts of scattered light from the exciting light frequency are situated in the gigahertz range. We show that the frequency shifts increase with decrease in the nanoparticle sizes.     

Vibrational density of states of hen egg white lysozyme

The resonant Raman scattering in GeSi/Si structures with GeSi quantum dots has been analyzed. These structures were formed at various temperatures in the process of molecular-beam epitaxy. It has been shown that Raman scattering spectra recorded near resonances with the E₀ and E₁ electronic transitions exhibit the lines of Ge optical phonons whose frequencies differ significantly from the corresponding values in bulk germanium. In the structures grown at low temperatures (300–400°C), the phonon frequency decreases with increasing excitation energy. This behavior is attributed to Raman scattering, which is sensitive to the size of quantum dots, and shows that quantum dots are inhomogeneous in size. In the structures grown at a higher temperature (500°C), the opposite dependence of the frequency of Ge phonons on excitation energy is observed. This behavior is attributed to the competitive effect of internal mechanical stresses in quantum dots, the localization of optical photons, and the mixing of Ge and Si atoms in structures with a bimodal size distribution of quantum dots.     

Guest-host coupling and anharmonicity in clathrate hydrates

We present a review of our work on the dynamics of clathrate hydrates (gas hydrates). The experimental results obtained with inelastic neutron scattering are compared with molecular-dynamics calculations. The vibrations of the guest molecules and their coupling to the cages is found to depend critically on the size, shape and electrostatic properties of the encaged guest. Atoms like xenon, that are large enough to fill the cages, show close-to-harmonic behaviour and couple strongly to the cage vibrations. Small atoms and molecules fully explore the anharmonicities of the potential within the cage, in particular at low frequencies and low temperatures. Their dynamic response is broad in energy and they couple weakly to the cage vibrations. The relevance of the microscopic dynamics for cage stability and the glass-like thermal conductivity is discussed. We equally place the observed dynamic peculiarities into the broader context of vibrations in disordered systems. Raman spectroscopic results on internal guest vibrations at high frequencies reflect also the influence of guest-host interactions and are discussed in the framework of the loose-cage tight-cage model.Received: 1 January 2003, Published online: 30 October 2003PACS: 82.75.-z Molecular sieves, zeolites, clathrates, and other complex solids - 61.46. + w Nanoscale materials: clusters, nanoparticles, nanotubes, and nanocrystals - 63.20.-e Phonons in crystal lattices     

Enhancement of Raman scattering by deformation of microparticles

Raman scattering on deformed droplets levitated in an acoustic levitator and produced by a vibrating-orifice aerosol generator were investigated. Our samples experiments were diethyl hexyl sebecate (DEHS) droplets in the millimeter-size range and ethanol droplets in the size range 50-100 microm. The C-H stretching region from 2800 to 3100 cm(-1) was investigated. We found that the Raman intensity measured by a scattering angle of 90 degrees depended on the shape of the droplets. Raman scattering on spherical droplets was smaller than scattering on spheroidal droplets with the same volume. Similar results were observed for the fluorescence signal of Rhodamine 6G-doped DEHS droplets.     

Low-frequency laser spectroscopy of cylindrical nanoparticle suspensions

A theory of generation of anti-Stokes radiation on the eigenvibrations in a suspension of cylindrical nanoparticles in the field of two copropagating electromagnetic pump waves has been developed. Surface ponderomotive forces are shown to induce acoustic vibrations and dipolemoments of nanoparticles at the anti-Stokes frequency. Under these conditions, the scattering efficiency depends on the dielectric characteristics of the solution and the acoustic parameters of the liquid and solid fractions of the suspension. Experiments on stimulated low-frequency Raman scattering of laser radiation in aqueous suspensions of tobacco mosaic virus in a buffer solution have been performed. A coherent signal of the Stokes component with a frequency shift of ≈60GHz is detected; this value is in good agreement with the estimated frequency shift for stimulated excitation of eigenvibrations of cylindrical nanoparticles in a liquid: ≈50 GHz.     

Quantum confinement effect in the vibrational spectrum of CdSxSe1−x quantum dots in a fluorophosphate glass matrix

The vibrational spectra of mixed cadmium sulfoselenide nanocrystals in a fluorophosphate glass matrix are investigated by Raman spectroscopy. The asymmetry of the lines of the fundamental modes of nanocrystals is experimentally observed in the region of lattice vibrations, which is interpreted as a quantum confinement effect. In the framework of the model of confined phonons, the contribution of the band states to the Raman scattering spectrum is calculated and the size of nanocrystalline regions is estimated. The results obtained are in good agreement with the data on the low-frequency Raman scattering in these objects.     

Excitation spectroscopy,Raman scattering and the temperature dependence of the luminescence in highly excited red HgI2

The luminescence of red HgI₂ is investigated as a function of temperature, excitation intensity and wavelength. At high excitation intensity and low temperature an “M-band” emission dominates. This M-band is assigned to biexciton decay and bound exciton scattering with acoustic phonons (“acoustic wing”), this assumption being supported by the results of excitation spectroscopy. The energy of the biexciton is determined to be (4661 ± 1) meV. From the evaluation of Raman spectra, the phonon energies (1.9, 3.1 and 14.0 ± 0.2) meV are found. At higher temperatures two lines are observed, one of which is ascribed to exciton-free carrier scattering. Position and line shape are in good agreement with theoretical results. The other emission line is found to be due to scattering involving excitons or carriers bound to lattice defects.