Two-phonon Raman scattering in GaAs

The second-order Raman Spectrum of GaAs has been measured at room temperature by using an argon ion laser with Brewster's angle configuration. A number of critical points have been interpreted by considering neutron inelastic scattering work and detailed critical-point analysis in Ge. The Γ₁ component is the strongest in the spectrum where overtone scattering is dominant. Combination scattering has been observed in the energy region between 300 and 350 cm^?1for both Γ₁ and Γ₁₅ components. The second-order Raman spectrum is compared with the two-phonon overtone Raman intensity, calculated from neutron diffraction data. In the low frequency region, the Raman spectrum shows directly the one-phonon density of states of the TA phonon.     

On the curve of the density of phonon states for cubic boron nitride (from the results of photoluminescence measurements)

The fine structure of the phonon wing associated with the zero-phonon line (ZPL) of the BN1 center in the cubic boron nitride is analyzed in comparison with the structure of the phonon wing of the luminescence center at 3.188 eV in diamond, the second-order Raman scattering spectrum, and the theoretically calculated densities of phonon states of the c-BN compound. Taking into account the similarity of the structures of the phonon wings in the spectra of the above centers and the previously made assumptions that the structure of the phonon wing of the center at 3.188 eV is due to the specific features in the density of phonon states of diamond, it is assumed that, in the observed density of phonon states of cubic boron nitride, the critical points are represented by the specific features of the structure of the phonon wing associated with the zero-phonon line (at 3.294 eV) of the BN1 luminescence center. In turn, these latter specific features coincide accurate to within 5–10cm^?1 with the theoretically calculated lattice vibrations of the c-BN compound and the experimental data obtained from the second-order Raman spectra.     

Evolution of the symmetry of intermediate phases and their phonon spectra during the topochemical conversion of silicon into silicon carbide

A symmetry analysis of the crystal structure and the phonon spectrum during continuous topochemical conversion of silicon into silicon carbide has been carried out. The transformation of the symmetry of phonons at high-symmetry points of the Brillouin zone upon the transition from the initial cubic structure of silicon (diamond) through an intermediate cubic structure of silicon carbide to the trigonal structure of SiC has been determined. The selection rules for the infrared and Raman spectra of all the three phases under investigation have been established.     

Theoretical polarization dependence of the two-phonon double-resonant Raman spectra of graphene

The experimental Raman spectra of graphene exhibit a few intense two-phonon bands, whichare enhanced through double-resonant scattering processes. Though there are manytheoretical papers on this topic, none of them predicts the spectra within a single model.Here, we present results for the two-phonon Raman spectra of graphene calculated by meansof the quantum-mechanical perturbation theory. The electronic and phonon dispersions,electronic lifetime, electron-photon and electron-phonon matrix elements, are all obtainedwithin a density-functional-theory-based non-orthogonal tight-binding model. We studysystematically the overtone and combination two-phonon Raman bands, and, in particular,the energy and polarization dependence of their Raman shift and intensity. We find thatthe ratio of the integrated intensities for parallel and cross polarized light for alltwo-phonon bands is between 0.33 and 0.42. Our results are in good agreement with theavailable experimental data.     

High resolution electron energy loss spectroscopy surface studies of hydrogenated detonation nano-diamond spray-deposited films

Nano-diamond films composed of 3–5 nm grains prepared by the detonation method and spray deposited onto silicon substrates were examined by high resolution electron energy loss spectroscopy (HR-EELS), Raman spectroscopy and transmission electron microscopy. The HR-EEL spectrum of the annealed and hydrogenated films displays dominant C–H losses at 360–365 meV; the diamond optical phonon and its overtones. These results suggest that the films reveal well defined hydrogenated diamond surfaces on the nanometric scale. Detailed analysis of the diamond optical phonon overtone revealed a red-shift of the basic C–C vibration by 5 meV. We attribute this shift to a phonon quantum confinement effect detected by HR-EELS spectroscopy.     

Two phonon density of states of partially disordered crystal NH4I

Two phonon density of states of NH₄ have been computed with the help of deformation dipole model at room temperature. The results have been compared with the available experimental Raman Spectrum and peak position. It has been shown that in addition to single phonon process which is dominant, the two-phonon density of states also contribute to the Raman Intensity in a partially disordered crystal.     

Two-Phonon States and Overtone Delocalization in One-Dimensional Systems of Oscillators: Vibrational Spectroscopy of a NO Adsorbate Row Structure

We report on a strong overtone delocalization in one-dimensional systems due to interaction with the two-phonon state. Whereas this interaction leads to small continuous shifts in comparable two-dimensional systems we find a discontinuous shift with bond anharmonicity in one dimension. As a consequence no overtone features can be observed in the spectral function. Experimentally, the phonon dispersion for a quasi-one-dimensional adsorbate system, molecular NO rows in the well-ordered (NO+O)-(2x1) phase on Ru(001), has been mapped out using electron energy loss spectroscopy. The internal NO mode shows a strong band dispersion of 110 cm(-1) along the molecular row. In the region of its overtone the spectra show a peak structure and a nonvanishing background which is interpreted as an overtone-modified two-phonon state.     

Anomalous two-phonon absorption in diamond nanocrystals embedded in amorphous carbon

Observation of anomalously strong IR absorption are reported in the region of two-phonon diamond frequencies in amorphous hydrogenated carbon films grown by cosputtering graphite and copper in a plasma. Up to five structural elements of bands having frequencies close to or coinciding with the figures quoted in the literature for two-phonon absorption bands in bulk diamond were observed. This suggests the presence of diamond nanocrystals in the grown layers. Observation of two-phonon absorption in thin films is in itself remarkable because of the smallness of its coefficient in bulk diamond. An estimate of the absorption coefficient in the dominant band at 2140 cm^?1 yields about 200 cm^?1, which exceeds by more than an order of magnitude that for bulk diamond. This can be assigned to an anomalous enhancement of the two-phonon absorption coefficient due to phonon confinement in the small diamond particles nucleated in the amorphous carbon matrix. An estimate of these inclusions from the band width yields about 20 Å. The reasons for the catalytic activity of copper in diamond nucleation are analyzed.     

Structure comparison of Orpiment and Realgar by Raman spectroscopy

Raman spectroscopy was used to characterize and differentiate the two minerals, Orpiment and Realgar, and the bands related to the mineral structure. The Raman spectra of these two minerals are divided into three sections: (a) 100–250?cm^?1 region attributed to the sulfur–arsenic–sulfur bending vibrational modes; (b) 250–450?cm^?1 region due to the arsenic–sulfur stretching vibration; and (c) 450–850?cm^?1 region assigned to overtone and combination bands. A total of 14 Raman bands for the spectrum in the 1600–100?cm^?1 region were observed. The significant differences between the minerals Orpiment and Realgar are observed by Raman spectroscopy. Realgar shows the typical bands observed at 340, 268, 228, and 218?cm^?1, and the special bands at 379, 289, 200, 176, and 102?cm^?1 for Orpiment are observed. The additional bands in 850–450?cm^?1 region are only observed for the mineral Orpiment, which may be attributed to overtone and combination bands in the Raman spectrum. The variation in band positions is dependent upon the structural symmetry, arsenic–sulfur bond distances, and angles. Moreover, another cause for the difference is the effect of the intermolecular forces and to the strong coupling between close lying external and internal modes. The difference of these two minerals structure induce tremendous diversity on Raman spectra, so Raman spectroscopy offers the information on the molecular structure of the minerals Orpiment and Realgar.     

Resonance Raman scattering of excitonic polaritons by LO and acoustic phonons in ZnTe

We have observed dispersive two-phonon Raman scattering of polaritons by LO and acoustic phonons near the lowest exciton state of ZnTe. From the Stokes shifts of these Raman lines, it has been found that the scattering process switches from an acoustic phonon followed by one LO phonon to the reversed one: a LO phonon followed by an acoustic one.     

Anomalous low-frequency phonons in ZrB<Subscript>12</Subscript>

The influence of pressure and temperature on low-frequency lines (100–300 cm^–1) in Raman spectra of ZrB₁₂ and LuB₁₂ single crystals has been investigated. These spectral features have been identified as one-phonon and two-phonon excitations of the acoustic branches of the phonon spectrum. It has been found that the observed spectra of ZrB₁₂ single crystals are more structured and indicate the development of phonon anomalies with a decrease in the temperature. Despite the fact that the low-frequency features in the phonon spectrum of ZrB₁₂ are characterized by a high value of the isothermal Grüneisen parameter, their isobaric Grüneisen parameter has a negative value. This indicates large contributions from the fourth-order anharmonicity, which significantly exceed the volume effects. The appearance of narrow lines in the frequency range from 155 to 175 cm^–1 at temperatures T < 100 K suggests the possibility of a structural transition with an incomplete softening of the lattice.     

Synthesis of w-CdS quantum dots and discovery of intense sub band emission owing to longitudinal optical phonons

Cadmium sulfide (CdS) quantum dots (QDs), capped with cetyltrimethylammonium bromide (CTAB), and was synthesized as stable, aqueous, colloidal nanofluid. A series of nine intense, well-resolved emission lines between 400 and 750 nm were observed for the first time when exciting the CdS QDs nanofluid with a 355-nm high energy pulsed Nd:YAG laser radiation. The energy separation between any two successive emission lines equals to the characteristic overtone energy of 295 cm⁻¹ of the longitudinal optical phonon of CdS QDs. In addition, recording the PL spectrum by using a xenon broad band light source resulted in the observation of this characteristic overtone energy of 295 cm⁻¹. In agreement with this photoluminescence characteristic, Raman spectrum exhibited four prominent Stokes lines with Raman shift equal to and multiple of 295 cm⁻¹. Transmission electron microscopy investigation showed that the CdS QDs were spherical with hexagonal wurtzite structure and had a size in the range of 5–10 nm.     

Study of porous silicon structure by Raman scattering

In this paper, the effect of etching time on light emitting porous silicon has been studied by using Raman scattering. Enhancement of Raman intensity by increasing the porosity is observed. Also there is a red shift, about 4 cm⁻¹, from the Raman peak of crystalline silicon to that of porous silicon. The phonon confinement model suggests the existence of spherical nanocrystalline silicon with diameter around 7 nm. But SEM images show that the samples have a sheetlike structure that confines phonons in one dimension. This should not cause any shift in their Raman spectra. It is suggested that the observed Raman peak shift is due to the spherical nanocrystals on the surface of these sheets.     

Two-phonon absorption in InP and GaP

Far-infrared absorption in crystals of GaP and InP was investigated using a high-resolution Fourier-transform spectrometer. The two-phonon absorption was found to be very similar in these two materials. Van Hove singularities on the GaP spectrum were identified with the aid of calculated two-phonon sum and overtone density-of-states curves. The analysis of the InP spectrum was based on its homology to GaP. Many of the prominent features of the absorption spectra are assigned to pairs of phonons on the hexagonal face of the Brillouin zone while phonon pairs at Γ, X and L generally contribute only minor features to the spectra.     

Theory of two-phonon modes in layered charge-density-wave systems

A theoretical model with electron-phonon and anharmonic interactions is proposed to explain the two-phonon mode observed in the Raman spectra of layered transition metal dichalcogenides, which exhibit charge density wave (cdw) phase transition. The phonon self-energy, which involves the electron response function and the two-phonon Green’s function, is calculated using the double-time Green’s function formalism. It is shown that in these low-dimensional systems there exists an anharmonicity-mediated two-phonon mode in the phonon spectral function both in the normal and in thecdw phases. In the normal phase since the phonon Raman scattering proceeds through a single optic phonon the calculations are carried out for zero wave vector and hence the contribution of the electron response function to the self-energy vanishes. On the other hand explicit evaluation of the two-phonon Green’s function shows that the frequency of the two-phonon mode is twice that of the Kohn anomaly phonon and decreases with decreasing temperature. The strength of two-phonon peak is found to be comparable to that of the original optic phonon. In thecdw phase the phonon which enters into the Raman scattering is taken to be the one with thecdw wave vectorQ, which when zone-folded becomes equivalent to zero wave vector. The evaluation of the electron response function in this phase generates a phonon corresponding to thecdw-amplitude mode. The two-phonon Green’s function is assumed to be of similar form as in the normal phase. The spectral function evaluated at zero temperature shows a weak two-phonon peak besides the prominentcdw-amplitude mode. Numerical results are presented for the system 2H-NbSe₂ and are found to be in qualitative agreement with the experimental data.     

Raman scattering by silicon

Reflection Raman spectroscopy has been performed on silicon at room temperature. One-phonon fine structure, which has been predicted by Cowley and observed in part by Wright et al., is fully obtained. Two-phonon structure is also obtained, which includes the most intense broad band observed by Parker et al. and weak broad bands not observed by them. One- and two-phonon structures reported here are very similar in shape to the ones predicted by Cowley by considering the anharmonicity of the lattice forces.     

Two-phonon bound states in imperfect crystals

The question of the occurrence of two-phonon bound states in imperfect crystals is investigated. It is shown that the anharmonicity mediated two-phonon bound state which is present in perfect crystals gets modified due to the presence of impurities. Moreover, the possibility of the occurrence of a purely impurity mediated two-phonon bound state is demonstrated. The bound state frequencies are calculated using the simple Einstein oscillator model for the host phonons. The two-phonon density of states for the imperfect crystal thus obtained has peaks at the combination and difference frequencies of two host phonons besides the peaks at the bound state frequencies. For a perfect crystal the theory predicts a single peak at the two-phonon bound state frequency in conformity with experimental observations and other theoretical calculations. Experimental data on the two-phonon infrared absorption and Raman scattering from mixed crystals of GA_1−c Al _c P and Ge_1−c Si _c are analysed to provide evidence in support of impurity-mediated two-phonon bound states. The relevance of the zero frequency (difference spectrum) peak to the central peak observed in structural phase transitions, is conjectured; This work is a part of the thesis to be submitted by one of the authors (SS) in partial fulfilment of the degree of Doctor of Philosophy to Utkal University, Bhubaneswar, India.     

Transformations of the Spectrum of an Optical Phonon Excited in Raman Scattering in the Bulk of Diamond by Ultrashort Laser Pulses with a Variable Duration

JETP Letters - A spontaneous Raman signal at the frequency of the triply degenerate optical phonon of diamond is observed in the photoluminescence spectrum under the pre-filamentation excitation of...     

Second order Raman spectrum of MoS2

The second order Raman spectra of a layer compound MoS₂ have been measured. Features characteristic of a two-dimensional phonon density of states curve have been observed. Most of the critical points in the second order spectrum are identified.     

空间限制与应变对发光多孔硅喇曼光谱的影响

发光多孔硅的喇曼光谱在５２０ｃｍ^－１附近呈现一锐峰，峰位的红移随多孔度的增大而增大采用微晶模型拟合喇曼谱的线形，发现除了光学声子的空间限制效应，硅单晶的应变对峰位的移动也有显著贡献。通过谱形的拟合估算了硅微粒的应变，与已报道的Ｘ射线衍射结果相一致。在多孔硅的喇曼光诸中没有观察到起源于非晶硅的光散射信号。 关键词：