Broadband terahertz time-domain spectroscopy and low-frequency Raman scattering of glassy polymers: Boson peak of PMMA

The low-energy vibrational properties of polymethyl methacrylate (PMMA) were studied by terahertz time-domain spectroscopy and Raman scattering. The real and imaginary parts of a complex dielectric constant were accurately determined in the frequency range from 0.2 to 5.0 THz. The imaginary part of the dielectric constant shows a line-shape similar to the imaginary part of the Raman susceptibility measured by Raman scattering. These two spectra show broad peaks at about 2.3 THz. We also separately determined the Raman and far-infrared light-vibration coupling constants of the PMMA using the vibrational density of states determined by cold neutron inelastic scattering in the literature.     

Raman spectroscopic study of SbxSe100−x phase-separated bulk glasses

The structure of Sb_xSe_100−x bulk glasses is investigated with the aid of Raman scattering over a wide composition range. The Raman spectra of the glasses exhibit unusual features when compared with other structurally similar binary glasses, owing to the phase separation of the present glasses in a certain composition range. The evolution of the Raman spectra and the depolarization ratio of the polarized and depolarized Raman intensities are consistent with the phase separation effect. The present findings are discussed alongside with calorimetric data from the literature that have been used up to now to extract structural information in an indirect way. The capability of Raman scattering as a tool for investigating phase separation in homogeneous media is demonstrated.     

Raman study of lattice dynamics in quasicrystals

We present the first Raman investigation of icosahedral quasicrystals. Broad structured bands in the energy range up to ~500 cm^− 1 have been observed in a series of AlCuFe, AlPdMn and AlPdRe systems. Original information on the vibrational density of states g(ω) was obtained for AlPdRe; for AlCuFe and AlPdMn estimated g(ω) shows a good agreement with the previous neutron results, but demonstrates finer structure. Strong increase in the parameter of electron-vibrational coupling for the low-energy vibrations and its correlation with changes in electronic conductivity has been observed in the series from AlCuFe to AlPdRe. This suggests the increase of the degree of localization for these vibrational excitations and involved electronic states.     

Analysis of waveguide silica glasses using Raman microscopy

A spectroscopic method to determine dopant concentrations in silicas used in silica on silicon planar waveguides has been developed. Raman spectroscopic measurements in the range 740 cm⁻¹–1370 cm⁻¹ of cross-sections of the glass layers identified correlations between simple, rapidly calculated, spectral features related separately to each of the three dopants, boron, phosphorous and germanium, and the wt% analyses results for these dopants from inductively coupled plasma mass spectrometry (ICP-MS) measurements on fragments from the respective wafers. The calibration wafers comprised a set of monitor wafers with dopant concentrations spanning the ranges used in devices. The Raman-based analyses were able to determine boron and phosphorous wt% s in boro-phosphosilicate cladding glasses with accuracies of ≈0.1 wt% and germanium wt% s in core glasses with an accuracy of at least ≈0.3 wt% (small batch size). The method, which performed successfully in blind tests, provides a spatially resolving and rapid alternative to ICP-MS analyses of monitor wafers. Exploratory face-on measurements were performed on device wafers. Spectra of the cladding, core and underlayer were obtained from AWG samples. The effects of the confocal volume’s finite size and refractive index differences were observed. Exploratory measurements using UV Raman excitation showed potential advantages for cladding glass analyses.     

Raman spectra and structure of sodium aluminogermanate glasses

Polarized Raman spectra of x NaAlO₂·(100 ? x) GeO₂ glasses (x = 0, 5, 10, 15, 20, 25, 33, 42, and 50) are presented. Analyses of the Raman data indicate that the aluminogermanate glasses have three-dimensional network structures consisting of interconnected AlO₄ and GeO₄ tetrahedra; Na⁺ ions are present in cavities and charge balance the Al³⁺ ions. Systematic changes are observed in the frequencies, intensities and polarization characteristics of spectral bands with variations in the NaAlO₂ content of these glasses. The antisymmetric stretching mode [ν_as (TOT), where T = Al, Ge] in the high-frequency region of the spectra (800–1000 cm^?1) appears as a doublet consisting of well-defined bands in the spectra of glasses along the entire join. Both components of the high-frequency doublet shift to a lower frequency with increasing NaAlO₂ content, indicating that the ν_as (GeO₄) and ν_as(AlO₄) stretching modes are coupled. The variations in the TO force constants and TOT bond angles with change in composition most likely cause the bands to shift. The frequencies of the Raman bands of sodium aluminogermanate glasses are compared with those of the corresponding bands in isostructural sodium gallogermanate glasses. On the basis of this comparison, the origin and delocalization of the vibrational modes producing characteristic Raman bands in the spectra of these glasses are discussed. The changes observed in the Raman spectra of aluminogermanate glasses with variation in NaAlO₂ content are analogous to those observed in the spectra of glasses along the NaAlO₂SiO₂ join.     

Structural development in Ge-rich Ge–S glasses

The Raman spectra of Ge–S glasses in the Ge-rich region from Ge 33% to 46% have been investigated in order to know the structural development of the network glasses. From the detailed curve fits, we have found that there is an unassigned peak at 410 cm⁻¹ and it becomes larger with increasing Ge composition. To clarify the structural origin of the peak, we virtually constructed the atomic arrangement of the glassy state starting from the crystalline state through the liquid state and changed the composition gradually depleting the medium in sulfur. From the consideration of the structural modeling and the atomic orbital theory, we suggest that single Ge–S chain is a probable structural origin of the peak.     

Structural study of sol-gel silicate glasses by IR and Raman spectroscopies

A study of the structure and bonding configuration of sol-gel silicate glasses by Raman and infrared spectroscopies is presented. Moreover, a review of the Raman lines and infrared bands assignment, the identification of the non-bridging silicon-oxygen groups and the ring structures are also demonstrated. The evolution of the changes of the bonding configuration in the composition and the stabilization temperature of the bioactive glasses is discussed in terms of the structural and textural characteristics of the glasses. Raman and infrared analyses contribute to the improvement in understanding of the local symmetry for sol-gel silicate glasses. infrared spectroscopy has allowed to identify the vibration bands of the hydroxyl groups associated with various configurations of the terminal silanol bonds on the glass surface and the free molecular water in the glass matrix. Raman analysis has provided an alternative method of quantifying the network connectivity grade and predicting the textural properties of the sol-gel silicate glasses.     

Structure of lead germanate glasses by Raman spectroscopy

Lead germanate glasses of the xPbO(1−x)GeO₂ compositions with x ranging from 0.200 to 0.625 have been synthesised and their crystallisation behaviour and vibrational properties studied by differential thermal analysis (DTA) and Raman spectroscopy. Raman spectra of the Pb₅Ge₃O₁₁ ceramics also have been measured and compared to lead germanate glass spectra and literature data on β-PbO. Ge atoms in low lead glasses are supposed to be surrounded by four to six oxygen atoms, while the high-lead glass (x=0.625) corresponding to stoichiometry of the Pb₅Ge₃O₁₁ ferroelectrics contains predominantly fourfold coordinated germanium. Structural resemblence of high-lead germanate glasses to the Pb₅Ge₃O₁₁ crystal is proposed rather than to β-PbO. The `boson' peak range in the spectra of lead germanate glasses is discussed taking into account the similarities of the spectra of glassy and crystalline Pb₅Ge₃O₁₁.     

Raman and optical reflection spectra of germanate and silicate glasses

Germanate and phosphosilicate glasses made in oxygen surplus conditions were studied by Raman and optical reflection methods. We found that the optical reflection spectra of the germanate glasses are quite similar to the one those of a GeO₂ crystal with the α-quartz structure. The reflection of phosphosilicate glasses is very close to silica glass-related spectra. Hence, the determining influence of the tetrahedral structure on reflection spectra is revealed. The Raman spectra of germanate samples are similar to those reported the one known in the literature. Octahedral entities, namely bands similar to stishovite vibration modes, were difficult to detect in phosphosilicate glasses through Raman spectroscopy.     

The structure of borate glasses studied by Raman scattering

Raman spectra of alkali and alkaline-earth borate glasses are reported. These spectra are used to discuss the molecular structure of the glasses. The influence of additions of Al₂O₃ on the structure of alkali borate glasses is also presented. The experimental evidence indicates that the same type of groups are present in borate glasses as in crystalline borates. The presence of tetraborate, metaborate, pyroborate and orthoborate groups in borate glasses is strongly suggested by the Raman spectra.     

Application of the constant stoichiometry grouping concept to the Raman spectra of Pb(PO3)2-TeO2 glasses

Pb(PO₃)₂-TeO₂ glasses in the whole range of glass composition were first obtained and their properties (refractive index, density, T_g and light scattering losses) were determined. Based on the vibrational spectroscopy data a new approach was applied to investigate the interactions of initial oxides in melts resulted in so-called constant stoichiometry groupings (CSGs) formation symbolizing intermediate range order in glasses. Vibrational spectra of glasses are interpreted as a superposition of unchangeable spectral forms (principal spectral components (PSCs)) belonging to CSGs: PbO · P₂O₅, TeO₂ · 2PbO · 2P₂O₅, TeO₂ · PbO · P₂O₅, TeO₂, and possibly 2TeO₂ · PbO · P₂O₅ and 6TeO₂ · PbO · P₂O₅. In this work Multivariate Data Analysis has been applied as the independent mathematical tool to decompose Raman spectra of glasses and reveal the number of PSCs. It is shown that application of factor analysis results in the same five PSCs that confirms our data obtained from the CSG concept. This concept allows also the prediction of the existence of unknown compounds, and correspondingly some crystals (TeO₂⋅ 2PbO⋅2P₂O₅ and others) were revealed by XRPD of the crystallized glasses. The CSG concept opens the way for elaboration of low scattering glasses as candidates for Raman amplifiers. It is shown that Pb(PO₃)₂-TeO₂ glasses with small content of TeO₂ are of interest to photonic technology.     

Resonant Raman Scattering near the Free‐to‐Bound Transition in Undoped p‐GaSe

Raman spectra of GaSe layered crystal have been measured using a He‐Ne laser and temperature tuning the free‐ to‐bound gap in the range 10‐290 K. Resonance enhancement of E″⁽²⁾ mode has been observed for both incident and scattered photon energies equal to the free‐to‐bound transition energy.     

Raman Scattering and X-Ray Diffraction Studies on Alkali-Metal Intercalated Clays

Abstract

Vermiculite and fluor-tetrasilicic mica were intercalated with alkali metals (Na, K and Rb) by vapor transport. X-ray and Raman scattering experiments were conducted to study the structure and lattice dynamics of the new clay compounds. When Rb and K atoms were intercalated to the host materials, superlattices were formed. In Na intercalated compounds, however, no superlattice x-ray diffraction peaks were found. Raman spectra exhibited drastic changes after alkali-metal intercalation, reflecting the structural changes found by our x-ray diffraction.     

Low‐Temperature Raman Scattering Spectra of GaSexS1‐x Layered Mixed Crystals

Raman scattering has been used to study the vibrational spectra of GaSe_xS_1‐x layered mixed crystals at 10 K. We report the frequency dependencies of different modes on composition x, with particular emphasis on A′₁⁽²⁾ (A_1g¹) and A′₁⁽⁴⁾ (A_1g²) intralayer compressional modes having low dispersion in the Brillouin zone. The appearance of additional bands is attributed to multimode behavior typically exhibited by mixed crystals of anisotropic compounds.     

Computational and Raman studies of phospho-tellurite glasses as ultrabroad Raman gain media

Molecular orbital calculations of two phospho-tellurite model clusters were performed to clarify the origins of the Raman bands in the Stokes region of over 1000 cm^− 1 in phospho-tellurite glasses. The Raman bands could be attributed to two components of 900-1050 cm^− 1 of symmetrical stretching vibrations of PO₄ units and 1050-1200 cm^− 1 of anti-symmetrical stretching vibrations of PO₄ units. It was also clarified that the top of the valence band of phospho-tellurite glasses consists of the lone pair electrons in a TeO_4 + 1 unit and the bottom of the conduction band of the glass consists of the antibonding hybrids of Te 5p and O 2p orbitals in the equatorial plane of a TeO₄ unit.We have developed new phospho-tellurite glasses which have the Raman gain peak of 30 times as large as silica glass or the Raman gain bandwidth of more than 1200 cm^− 1.     

The structure of borosilicate glasses studied by Raman scattering

Raman spectra of alkali and alkaline earth borosilicate glasses are reported. These spectra are used to discuss the molecular structure of the glasses. The influence of Al₂O₃ additions on the structure of borosilicate glass is also discussed. It is shown that the same type of groups are present in borosilicate glasses as in borate and silicate glasses. The presence of large borate groups such as tetraborate and metaborate groups is strongly suggested by the Raman spectra. It appears that boron ions are hardly taken up in the silicon-oxygen network. Our results suggest that the region of phase separation is larger than the region presently acknowledged.     

应用拉曼散射研究稀土钴氧化物的晶体结构

稀土钴氧化物的磁特性和输运性质强烈依靠稀土离子和它们的精细结构.通过Raman散射研究了稀土离子在两种结构中的作用.当R=La、Ce、Pr、Nd,时,RCoO_3化合物为立方结构(Pm~3m),而对于小离子半径(R=Sm、Eu、Gd和Dy),RCoO_3化合物存在于正交结构中[空间群为Pnma(D_(2h)~(16)),Z=4].按照其晶体结构和Raman行为,将RCoO_3化合物分成三个群体:一组包含La、Ce、Pr、Nd,另一组包含Sm、Eu、Gd、Dy,第三组包含Tm、Yb 、Lu 和Er.     

Non-Debye excess heat capacity and boson peak of binary lithium borate glasses

The non-Debye excess heat capacities of binary lithium borate glasses with different Li₂O compositions of x = 8, 14 and 22 (mol%) are investigated to understand origin of the boson peak. The low-temperature heat capacities are measured between 2 and 50 K by a relaxation calorimeter. The experimental non-Debye heat capacities with x = 14 is successfully reproduced using the excess vibrational density of states measured by inelastic neutron scattering. This finding indicates that the non-Debye heat capacities of lithium borate glasses originate from the excess vibrational density of states measureable by inelastic neutron scattering. Moreover, it is demonstrated that all of the excess heat capacity spectra lie on a single master curve by the scaling using boson peak temperature and intensity.     

Raman study of the structure of alkali germanosilicate glasses (I): Sodium and potassium metagermanosilicate glasses

Polarized and depolarized Raman spectra of sodium and potassium metagermanosilicate glasses are given. It is concluded from the Raman spectra that the structure of these glasses consists of metagermanosilicate chains in which both SiO₄ and GeO₄ tetrahedra are present, probably mixed in a random way.     

Resonance Raman Scattering of Br2 Doped Single-Walled Carbon Nanotube Bundles

Abstract

We have measured Raman spectra of bromine doped single-walled carbon nanotubes (SWNTs) using various laser lines to clarify the electronic states of the doped SWNT. In the case of evacuated sample after full doping, two breathing mode peaks were observed simultaneously by visible laser excitations. We assigned the higher frequency peak to the doped SWNT bundles, and the other peak to the undoped portions in the sample. Intensity ratio between them decreased with decreasing excitation energy, and in the infrared region, the breathing mode band of the doped bundle was not observed. These results can be explained by a simple rigid band model.