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Computational analysis of difference spectra between two analogous systems is a challenging issue, as reliable estimation of a tiny difference spectrum requires an extraordinary precision of the two original spectra. We have developed an alternative new method to calculate the difference spectra under background-free conditions, which greatly improved the efficiency of computation. In this paper, we report further improvement by using efficient parallel implementation and the time correlation formula based on time derivative quantities. As a consequence, the present work achieved further remarkable acceleration in the calculations of difference infrared and Raman spectra in the order of magnitude and thereby allowed us by analyzing these difference spectra at a practical cost of computation. [ABSTRACT FROM AUTHOR]

In this article, we present high-pressure experimental investigations on EuNbO4, an interesting technologically important material, using synchrotron based x-ray powder diffraction, Raman spectroscopy, and europium photoluminescence measurements up to 39.2, 31.6, and 32.4 GPa, respectively. All three techniques show the stability of the ambient monoclinic phase until 20 GPa. Beyond that, a pressure-induced structural phase transition takes place with the coexistence of two phases over a wide pressure range. The structure of the high-pressure phase has been determined as orthorhombic (space group: Imma) with a volume discontinuity of nearly 9% at the transition indicating the nature of transition to be first order. The high-pressure phase remains stable up to ∼40 GPa. The equation of state data for both phases have been determined, and the modulus of incompressibility indicates that the high-pressure phase with bulk modulus as 246(29) GPa is less compressible compared to the low-pressure phase having bulk modulus as 138(4) GPa. The transition involves a change in the coordination polyhedron around europium, increasing the coordination number from 8 in the fergusonite to 12 in the orthorhombic phase, while the coordination around niobium remains 4 in both the phases. All the 18 expected Raman modes in the fergusonite structure have been observed, and their variation as a function of pressure has been reported. The mode Grüneisen parameters for the observed Raman frequencies for monoclinic and orthorhombic phases have been determined. Europium photoluminescence spectra show drastic changes near the transition pressure, which point toward changes in the local environment around the europium ion. [ABSTRACT FROM AUTHOR]

The ordered structure of the MgO–ZnO alloy system is a versatile tunable optical material, which is promising for diverse optoelectronic applications. However, isovalent and isostructural alloy compositions of MgO–ZnO are generally unstable at ambient conditions. Using state-of-the-art ab initio evolutionary simulations, we predict and study the properties of stable phases of MgO–ZnO. We establish the dynamical stability of the predicted crystal structures through phonon and Raman spectroscopy. Detailed analyses of two of the most stable structures reveal highly tunable properties that could be explored for photonic and optical applications. [ABSTRACT FROM AUTHOR]

Among the small cation sized rare earth sesquioxides, the reported transition pressure of cubic Tm2O3 is ambiguous. Pressure induced structural phase transition in cubic Tm2O3 has been reinvestigated using the synchrotron X-ray diffraction, Raman spectroscopy, and ab initio density functional theory (DFT) calculations up to a pressure of 25 GPa. Both the X-ray diffraction and Raman spectroscopic measurements revealed an irreversible polymorphic structural phase transition from type-C cubic to type-B monoclinic at around 12 GPa, whereas the same is predicted to be 8 GPa from the density functional theory. The phase transition observed at 12 GPa is in contrast to the literature and the reasoning has been established by other studies, viz., Raman spectroscopy and DFT. A third order Birch-Murnaghan equation of state fit to the experimental compressibility curve yielded a zero pressure bulk modulus of 149(2) GPa with the pressure derivatives 4.8(5) for the parent cubic phase and 169(2) GPa with the pressure derivative 4 for the high pressure monoclinic phase, respectively. These values are in good agreement with the calculated bulk modulus of 146 and 151 GPa for the cubic and monoclinic phases, respectively. Raman modes for the monoclinic phase of Tm2O3 are measured and reported for the first time. The mode Grüneisen parameter of different Raman modes for both cubic and monoclinic phases of Tm2O3 has also been determined. The experimental results are correlated with changes in the density of states near the Fermi level, which are indicative of structural instabilities in the parent cubic structure. [ABSTRACT FROM AUTHOR]

In this study, we investigate the temperature dependence of low-frequency spectra in the frequency range of 0.3–200 cm−1 for ionic liquids (ILs) whose cations possess two systematically different cyclic groups, using femtosecond Raman-induced Kerr effect spectroscopy. The target ILs are bis(trifluoromethylsulfonyl)amide [NTf2]– salts of 1-cyclohexylmethyl-1-methylpyrrolidinium [CHxmMPyrr]+, 1-cyclohexylmethyl-3-methylimidazolium [CHxmMIm]+, N-cyclohexylmethylpyridinium [CHxmPy]+, 1-benzyl-1-methylpyrrolidinium [BzMPyrr]+, 1-benzyl-3-methylimidazolium [BzMIm]+, and N-benzylpyridinium [BzPy]+ cations. The aim of this study is to better understand the effects of aromaticity in the cations’ constituent groups on the temperature-dependent low-frequency spectral features of the ILs. The low-frequency spectra of these ILs are temperature dependent, but the temperature-dependent spectrum of [CHxmMPyrr][NTf2] is different from that of other ILs. While [CHxmMPyrr][NTf2] shows spectral changes with temperature in the low-frequency region below 50 cm−1, the other ILs also show spectral changes in the high-frequency region above 80 cm−1 (above 50 cm−1 in the case of [BzMPyrr][NTf2]). We conclude that the spectral change in the low-frequency region is due to both the cation and anion, while the change in the high-frequency region is attributed to the red shift of the aromatic ring librations. On the basis of the plots of the first moment of the spectra vs. temperature, we found that the first moment of the low-frequency spectrum of the IL whose cation does not have an aromatic ring is less temperature dependent than that of the other ILs. However, the intrinsic first moment, the first moment at 0 K, of the low-frequency spectrum is governed by the absence or presence of a charged aromatic group, while a neutral aromatic group does not have much influence on determining the intrinsic first moment. [ABSTRACT FROM AUTHOR]

The correlations between different quantum-mechanical degrees of freedom of molecular species dictate their chemical and physical properties. Generally, these correlations are reflected in the optical response of the system but in low-order or low-dimensionality measurement the signals are highly averaged. Here, we describe a novel four-dimensional coherent spectroscopic method that directly correlates within and between the manifold of electronic and vibrational states. The optical response theory is developed in terms of both resonant and non-resonant field-matter interactions. Using resonance to select coherences on specific electronic states creates opportunities to directly distinguish coherent dynamics on the ground and electronically excited potentials. Critically, this method is free from lower-order signals that have plagued other electronically non-resonant vibrational spectroscopies. The theory presented here compliments recent work on the experimental demonstration of the 4D spectroscopic method described. We highlight specific means by which non-trivial effects such as anharmonicity (diagonal and off-diagonal), mode-specific vibronic coupling, and curvature of the excited states manifest in different projections of the 4D spectrum. [ABSTRACT FROM AUTHOR]

Direct synthesis of vertically aligned metallic single-walled carbon nanotubes (m-SWCNT forests) is a difficult challenge. We have successfully synthesized m-SWCNT forests using faceted iron platinum-gold catalysts epitaxially grown on a single crystalline magnesium oxide substrate. The metallic content of the forests estimated by Raman spectroscopy reaches 90%. From the standpoint of growth rate of the forests, the growth mechanism is probably based on the catalyst of solid state. It is suggested that preferential growth of m-SWCNTs is achieved when both factors are satisfied, namely, {111} dominant octahedral facet and ideal size (fine particles) of FePt particles. [ABSTRACT FROM AUTHOR]

Gd-doped ZnO thin films were prepared using pulsed laser deposition at different oxygen pressures and varied Gd concentrations. The effects of oxygen deficiency-related defects on the Gd incorporation, optical and structural properties, were explored by studying the impact of oxygen pressure during deposition and post-growth thermal annealing in vacuum. Rutherford Backscattering Spectrometry revealed that the Gd concentration increases with increasing oxygen pressure for samples grown with the same Gd-doped ZnO target. Unexpectedly, the c-lattice parameter of the samples tends to decrease with increasing Gd concentration, suggesting that Gd-defect complexes play an important role in the structural properties. Using low-temperature photoluminescence (PL), Raman measurements and density functional theory calculations, we identified oxygen vacancies as the dominant intrinsic point defects. PL spectra show a defect band related to oxygen vacancies for samples grown at oxygen deficiency. [ABSTRACT FROM AUTHOR]

The plasmonic responses of silver nanoparticle grating structures of different periods made on silver halide based electron microscope film are investigated. Raster scan of the conventional scanning electron microscope (SEM) is used to carry out electron beam lithography for fabricating the plasmonic nanoparticle grating (PNG) structures. Morphological characterization of the PNG structures, carried out by the SEM and the atomic force microscope, indicates that the depth of the groove decreases with a decrease in the grating period. Elemental characterization performed by the energy dispersive spectroscopy and the x-ray diffraction shows the presence of nanoparticles of silver in the PNG grating. The optical characterization of the gratings shows that the localized surface plasmon resonance peak shifts from 366 to 378 nm and broadens with a decrease in grating period from 10 to 2.5 μm. The surface enhanced Raman spectroscopy of the Rhodamine-6G dye coated PNG structure shows the maximum enhancement by two orders of magnitude in comparison to the randomly distributed silver nanoparticles having similar size and shape as the PNG structure. [ABSTRACT FROM AUTHOR]

We have developed a single-shot Raman spectroscopy experiment to study at the molecular level the initiation mechanisms that can lead to sustained detonation of a triaminotrinitrobenzene-based explosive. Shocks up to 30 GPa were generated using a two-stage laser-driven flyer plate generator. The samples were confined by an optical window and shock pressure was maintained for at least 30 ns. Photon Doppler Velocimetry measurements were performed at the explosive/window interface to determine the shock pressure profile. Raman spectra were recorded as a function of shock pressure and the shifts of the principal modes were compared to static high-pressure measurements performed in a diamond anvil cell. Our shock data indicate the role of temperature effects. Our Raman spectra also show a progressive extinction of the signal which disappears around 9 GPa. High-speed photography images reveal a simultaneous progressive darkening of the sample surface up to total opacity at 9 GPa. Reflectivity measurements under shock compression show that this opacity is due to a broadening of the absorption spectrum over the entire visible region. [ABSTRACT FROM AUTHOR]

Dense nitrogen exhibits fascinating molecular and extended polymorphs as well as an anomalous melt maximum at high temperatures. However, the exact solid-liquid phase boundary is still the subject of debate, as both creating and probing hot dense nitrogen, solid and fluid alike, poses unique experimental challenges. Raman studies of nitrogen were performed to investigate the melting curve and solid-solid phase transitions in the pressure-temperature range of 25 to 103 GPa and 300 to 2000 K. The solid-liquid phase boundary has been probed with time-resolved Raman spectroscopy on ramp heated nitrogen in diamond anvil cell (DAC), showing a melting maximum at 73 GPa and 1690 K. The solid-solid phase boundaries have been measured with spatially resolved micro-confocal Raman spectroscopy on resistively heated DAC, probing the δ-ε phase line to 47 GPa and 914 K. At higher pressures the θ-phase was produced upon a repeated thermal heating of the ζ -phase, yet no evidence was found for the ι-phase. Hence, the present results signify the path dependence of dense nitrogen phases and provide new constraints for the phase diagram. [ABSTRACT FROM AUTHOR]

Vibrational properties of isoviolanthrone are investigated by Raman scattering at pressures up to 30.5 GPa and room temperature. A complete characterization of phonon spectra under pressure is given for this material. The onset of a phase transition at 11.0 GPa and the formation of a new phase above 13.8 GPa are identified from both the frequency shifts and the changes in the full width half maxima of the intra- and internal modes. The transition is proposed to result from the changes of intra- and intermolecular bonding. The tendencies of the intensity ratios with pressure are in good agreement with the pressure dependence of the resistance at room temperature, indicating that the phase transition may be an electronic origin. The absence of the changes in the lattice modes indicates that the observed phase transition is probably a result of the structural distortions or reorganizations. The reversible character of the transition upon compression and decompression is determined in the entire pressure region studied. [ABSTRACT FROM AUTHOR]

Raman investigations were carried out in the low-frequency and amide I regions on lysozyme aqueous solutions in absence and presence of trehalose. Raman spectroscopy gives the unique opportunity to analyze the protein and solvent dynamics in the low-frequency range while monitoring the unfolding process by capturing the spectrum of the amide I band. From the analysis of the quasielastic intensity, a dynamic change is firstly observed in a highly hydrated protein, around 70 °C, and interpreted in relation with the denaturation mechanism of the protein. The use of heavy water and partly deuterated trehalose gives clear information on protein–trehalose interactions in the native state of lysozyme (at room temperature) and during the thermal denaturation process of lysozyme. At room temperature, it was found that trehalose is preferentially excluded from the protein surface, and has a main effect on the tetrahedral local order of water molecules corresponding to a stiffening of the H-bond network in the solvent. The consequence is a significant reduction of the amplitude of fast relaxational motions, inducing a less marked dynamic transition shifted toward the high temperatures. Upon heating, interaction between trehalose and lysozyme is detected during the solvent penetration within the protein, i.e., while the native globular state softens into a molten globule (MG) state. Addition of trehalose reduces the protein flexibility in the MG state, improving the structural stability of the protein, and inhibiting the protein aggregation. [ABSTRACT FROM AUTHOR]

Structural stability of a transparent conducting oxide CuLaO2 at high pressures is investigated using in-situ Raman spectroscopy, electrical resistance, and x-ray diffraction techniques. The present Raman investigations indicate a sequence of structural phase transitions at 1.8 GPa and 7GPa. The compound remains in the first high pressure phase when pressure is released. Electrical resistance measurements carried out at high pressures confirm the second phase transition. These observations are further supported by powder x-ray diffraction at high pressures which also showed that a-axis is more compressible than c-axis in this compound. Fitting the pressure dependence of unit cell volume to 3rd order Birch-Murnaghan equation of state, zero pressure bulk modulus of CuLaO2 is determined to be 154(25) GPa. The vibrational properties in the ambient delafossite phase of CuLaO2 are investigated using ab-initio calculations of phonon frequencies to complement the Raman spectroscopic measurements. Temperature dependence of the Raman modes of CuLaO2 is investigated to estimate the anharmonicity of Raman modes. © 2014 AIP Publishing LLC. [ABSTRACT FROM AUTHOR]

Structural relaxation of As-Se glasses through the glass-to-supercooled liquid transition interval is studied with temperature-modulated differential scanning calorimetry. It is shown that connectivity of glass network and long-term physical ageing change not only the full width at half maximum of the out-of-phase component of complex heat capacity, which is conventionally used for analysis, but also its asymmetry value. The latter is shown to carry very important information on the dynamic heterogeneity in glasses. Raman spectroscopy is used as complementary technique to reveal possible structural rearrangements in the investigated glass network. [ABSTRACT FROM AUTHOR]

Long known as a fully polarized band with a near vanishing depolarization ratio [ηs = 0.05, W. Holzer and R. Ouillon, Chem. Phys. Lett. 24, 589 (1974)], the 2ν5 Raman overtone of SF6 has so far been considered as of having a prohibitively weak anisotropic spectrum [D. P. Shelton and L. Ulivi, J. Chem. Phys. 89, 149 (1988)]. Here, we report the first anisotropic spectrum of this overtone, at room temperature and for 13 gas densities ranging between 2 and 27 amagat. This spectrum is 10 times broader and 50 times weaker than the isotropic counterpart of the overtone [D. Kremer, F. Rachet, and M. Chrysos, J. Chem. Phys. 138, 174308 (2013)] and its profile much more sensitive to pressure effects than the profile of the isotropic spectrum. From our measurements an accurate value for the anisotropy matrix-element |〈000020|Δα|000000〉| was derived and this value was found to be comparable to that of the mean-polarizability |〈000020| ...α |000000〉|. Among other conclusions our study offers compelling evidence that, in Raman spectroscopy, highly polarized bands or tiny depolarization ratios are not necessarily incompatible with large polarizability anisotropy transition matrix-elements. Our findings and the way to analyze them suggest that new strategies should be developed on the basis of the complementarity inherent in independent incoherent Raman experiments that run with two different incident-beam polarizations, and on concerted efforts to ab initio calculate accurate data for first and second polarizability derivatives. Values for these derivatives are still rarities in the literature of SF6. [ABSTRACT FROM AUTHOR]

The present study of deep level transient spectroscopy (DLTS) is focused on a comparison of the trap states in two types of Ge nanocrystallites (NCs)-insulator composites. The investigated systems were the dielectric matrices Al2O3 and SiO2 in which the Ge NCs were embedded. We have found couples of traps with related values of activation energies in both the Ge:Al2O3 and the Ge:SiO2 films. In the films with a relatively low Ge content (where only small NCs sized 3-5 nm could have been detected by means of Raman spectroscopy), we observed traps with an energy level ∼50 meV in the Ge:Al2O3 films and 120 and 50 meV in the Ge:SiO2 films. In both systems, we found that the electron traps have a small carrier capture cross-section (10-21-10-23 cm2). We have identified the levels of the traps to be the quantum confinement levels in the small Ge NCs. For samples of higher Ge contents, where the NC size reaches about 20 nm and where an appreciable portion of the dielectric matrix consists of amorphous Ge (α-Ge), we found traps with an energy of 0.22-0.24 eV in the Ge:Al2O3, and 0.26-0.27 eV in the Ge:SiO2 samples. We suggest that this peak in the charge DLTS (Q-DLTS) spectra is associated with a trap at the Ge-NC/α-Ge interface. We have also identified the energy position of a defect level in the Ge:Al2O3 layers, which lies 0.46-0.49 eV below the conduction-band edge of the Si substrate. [ABSTRACT FROM AUTHOR]

Raman spectroscopy provides rich optical signals that can be used, after data analysis, to assess if a graphene layer is pristine, doped, damaged, functionalized, or stressed. The area being probed by a conventional Raman spectrometer is, however, limited to the size of the laser beam (∼1 µm); hence, detailed mapping of inhomogeneities in a graphene sample requires slow and sequential acquisition of a Raman spectrum at each pixel. Studies of physical and chemical processes on polycrystalline and heterogeneous graphene films require more advanced hyperspectral Raman capable of fast imaging at a high spatial resolution over hundreds of microns. Here, we compare the capacity of two different Raman imaging schemes (scanning and global) to probe graphene films modified by a low-pressure plasma treatment and present an analysis method providing assessments of the surface properties at local defects, grain boundaries, and other heterogeneities. By comparing statistically initial and plasma-treated regions of graphene, we highlight the presence of inhomogeneities after plasma treatment linked to the initial state of the graphene surface. These results provided statistical results on the correlation between the graphene initial state and the corresponding graphene–plasma interaction. This work further demonstrates the potential use of global hyperspectral Raman imaging with advanced Raman spectra analysis to study graphene physics and chemistry on a scale of hundreds of microns. [ABSTRACT FROM AUTHOR]

Nanoscale spectroscopy and imaging, a hybrid technique that combines a scanning probe microscope (SPM) with spectroscopy, can provide nanoscale topographical, spectral, and chemical information of a sample. In recent years, developments in nanofabrication technology have dramatically advanced the field of nanospectroscopy for applications in various fields including nanoscale materials, electronics, catalysis, and biological systems. However, challenges in nanofocusing of light for excitation and extracting weak signals of individual molecules from the background signal persist in conventional nanoscale spectroscopy including tip-enhanced Raman spectroscopy, scanning near-field microscopy (SNOM/NSOM), and photoluminescence spectroscopy. This article reviews new approaches to design plasmonic SPM probes that improve important aspects of nanospectroscopy such as nanofocusing, far-to-near-field-coupling efficiency, background suppression, and ease of fabrication. The authors survey a diverse range of novel schemes to excite propagating surface plasmon polaritons on the probe surface to attain highly enhanced nanofocused light at the apex for nanoscale spectroscopies. These schemes include grating coupler configurations on the plasmonic SPM probes, aperture and apertureless plasmonic SNOM probes, nanostructured resonators coupled with a highquality- factor photonic cavity, interfacing of the optical fiber with plasmonic nanowires, and nanoparticle-coupled plasmonic nanowires. These innovative probes merge the field of fiber optics, plasmonics, quantum optics, and nanomaterials. The authors provide a perspective on new approaches that combine the advantages of these probes and have the potential for significant advancement in nanoscale imaging and other types of nanoscale spectroscopies including scanning quantum spin spectroscopy and scanning thermal imaging microscopy. [ABSTRACT FROM AUTHOR]

We have formulated the size and temperature dependence of the phonon relaxation dynamics for CdS, CdSe, Bi2Se3, and Sb2Te3 nanostructures based on the framework of bond order-length-strength correlation, core-shell configuration, and local bond averaging approach. The Raman shifts are correlated directly to the identities (nature, order, length, and energy) of the representative bond of the specimen without needing involvement of the Grüneisen mode parameters or considering the processes of phonon decay or multi-phonon resonant scattering. Quantitative information of the Debye temperature, the atomic cohesive energy, the reference frequencies from which the Raman shifts proceed, and the effective coordination numbers of the randomly sized particles, as well as the length and energy of the representative bond, has been obtained. It is clarified that the size-induced phonon softening arises intrinsically from the cohesive weakening of the undercoordinated atoms in the skin up to three atomic layers and the thermally derived phonon softening results from the thermally lengthening and weakening of bonds. Developed approach empowers the Raman technique in deriving quantitative and direct information regarding bond stiffness relaxation with applied stimuli such as coordination, mechanical, thermal, and chemical environment, which are crucial to practical applications. [ABSTRACT FROM AUTHOR]

High-density KTaO3 ceramics were synthesized and studied by means of microwave, terahertz, infrared, and Raman spectroscopies. The results were analyzed together with recently published radio-frequency data. [S. Glinsˇek et al., J. Am. Ceram. Soc. 94, 1368 (2011)] Three polar modes expected for the cubic structure were observed. As in single crystals, the lowest-frequency TO1 mode (soft mode) strongly softens on cooling, while the TO2 and TO4 mode frequencies do not change with temperature. The permittivity does not show any significant dispersion below the soft mode frequency and its value in the kHz and GHz range is mainly given by the intrinsic polar lattice modes contribution. The soft mode frequency agrees with the values found in single crystals; this indicates a negligible influence of the grain boundaries on the dielectric response in KTaO3 unlike in other ferroelectric or incipient ferroelectric perovskite ceramics. [ABSTRACT FROM AUTHOR]

Understanding of the origin of some of the intermediate frequency modes (IFMs) in the Raman spectrum of carbon nanotubes has remained controversial in the literature. In this work, through controlled introduction and elimination of defects in carbon nanotubes, we attempt to isolate the IFMs due to structural defects from that of the combination modes in single walled carbon nanotubes (SWCNTs). Our investigations on pristine and defect engineered SWCNTs using ion-irradiation, thermal annealing, and laser processing show systematic changes in the IFMs in the range 400-1200 cm-1 and its manipulation with the processing parameters. In particular, we found that the intensity of IFM at 929 cm-1 scale up with the increasing defect concentration, while that at 668 cm-1 follows opposite behavior. New IFM peaks were observed upon the creation of a controlled amount of structural defects through 30 keV N+ ion irradiation. Elimination of defects through vacuum annealing results into reduction of intensity of some IFMs identified as defect related, while the intensity of characteristic combination modes correspondingly increases. Our results show that the IFMs observed at 709, 805, 868, 926, and 1189 cm-1 are due to structural defects in the SWCNTs, while those in the range 400-550 cm-1 and at 669 cm-1 are due to the combination modes. Our x-ray photoelectron spectroscopy analysis on ion irradiated SWCNTs supports the Raman results. [ABSTRACT FROM AUTHOR]

Three-dimensional integration with through-silicon vias (TSVs) has emerged as an effective solution to overcome the wiring limit imposed on device density and performance. However, thermal stresses induced in TSV structures raise serious thermomechanical reliability concerns. In this paper, we analyze the near-surface stress distribution in a TSV structure based on a semi-analytic approach and finite element method, in comparison with micro-Raman measurements. In particular, the depth dependence of the stress distribution and the effect of elastic anisotropy of Si are illustrated to properly interpret the Raman data. The effects of the surface oxide layer and metal plasticity of the via material on the stress and Raman measurements are discussed. The near-surface stress characteristics revealed by the modeling and Raman measurements are important for design of TSV structures and device integration. [ABSTRACT FROM AUTHOR]

The photoluminescence (PL) of Si nanocrystals (Si-nc) embedded in fused silica has been investigated under simultaneous excitations by laser and low energy proton beam. Ionodegradation of the sample, characterized by a rapid decrease and a spectral blueshift of the PL emission has been observed. These effects are associated with the creation of non-radiative centers in the Si-nc. Micro-Raman spectroscopy analysis shows that the proton beam has not changed the average size of Si-nc, but has disturbed a fraction of Si-Si bonds inside the Si-nc, which is consistent with both simulations and direct measurements. A post-annealing performed at 400 °C for 1 h can restore the structural properties of the Si-nc, but only a part of their nominal PL emission intensity is recovered. Characterization of the damage induced by low energy proton irradiation reported in this paper makes the use of light ion beams relevant for the experimental investigation of nanostructured systems, such as ionoluminescence measurements. [ABSTRACT FROM AUTHOR]

The oxygen content and the local oxygen arrangement of laser processed YBa2Cu3O7-δ (YBCO) thin films grown on LaAlO3 substrates have been probed by micro-Raman spectroscopy On these films, channels for easy vortex motion have been laser written (LW) into the bridge constrictions by heat-induced, partial depletion of oxygen from the laser-illuminated areas of these films. Raman microscopy has been used to investigate and characterize the oxygen content and structure of the laser written channels. Direct evidence for local micro-structural changes in the film during the LW process is presented and the heat affected zone, surrounding the channel borders, has been mapped. [ABSTRACT FROM AUTHOR]

A Raman spectroscopic study of Na1/2Bi1/2TiO3-x%BaTiO3 (NBT-x%BT) single crystals with x = 0 and 5.6 has been performed as a function of temperature from 25 to 600 °C. The general features of the Raman spectra for the various compositions were similar over the region of the phase diagram investigated, with only subtle changes between rhombohedral (R), tetragonal (T) and cubic phases. The peaks were broad, with no significant narrowing on cooling through a phase transition. We find evidence of an oxygen octahedral rotational mode in the paraelectric state. On cooling near and below the ferroelectric Curie temperature, a gradual change in intensity of the A-O and B-O peaks occurred with decreasing temperature. Evidence of a ferroelectric → antiferroelectric transition was found near 200-250 °C, consistent with the onset of dispersion in the dielectric constant. The phase transition mechanism was discussed. The findings indicate the presence of a broad distribution of quasistatic local structural distortions, which only have subtle differences in the various average structures. [ABSTRACT FROM AUTHOR]

Polarized Raman spectroscopy has been employed to investigate the evolution of the microstructure of 0.67PbMg1/3Nb2/3O3-0.33PbTiO3 (PMN-33%PT) single crystal in the temperature range from -195 to 300 °C. The MA-MC-cubic transition sequence was observed in the microareas with MA-type (space group Cm) and MC-type (space group Pm) monoclinic structures. Interestingly, the MA-MC phase transition temperature exhibited remarkable microareal dependence due to the spatial inhomogeneity of polar nanoregions (PNRs). The MC-cubic phase transition took place at 155 °C in both microareas, which consisted well with previous reports. These results reveal that the phase transition in PMN-33%PT single crystal is closely related with the thermal dynamics of PNRs, which will be useful for understanding the microheterogeneity in this compound. [ABSTRACT FROM AUTHOR]

Rare-earth-doped fluorochlorozirconate (FCZ) and fluorobromozirconate (FBZ) glasses developed for fluorescence applications are analyzed, with particular attention paid to their phonon energy spectra. After thermal processing of as-made Eu-doped FCZ and FBZ glasses, Raman measurements show additional phonon bands at low phonon energies, indicating the formation of BaCl2 and BaBr2 nanocrystals, respectively. The phonon bands can be assigned to hexagonal, orthorhombic, or a mixture of both phases of BaCl2 and BaBr2 depending on the annealing conditions. Apart from line broadening, the Raman spectra of the orthorhombic nanocrystals agree well with those of BaCl2 and BaBr2 bulk crystals, while the metastable hexagonal phases of BaCl2 and BaBr2 are investigated only in appropriately treated FCZ and FBZ glasses, respectively. The experimental Raman spectra are compared to first principle studies of the phonon frequencies of the hexagonal and orthorhombic phases of both barium halides, showing good agreement. [ABSTRACT FROM AUTHOR]

Herewith we present the results of our studies on the effect of confinement on the solvation of ethyl alcohol in aqueous solutions using Raman spectroscopy of the O-H stretching band. Based on Gaussian-Lorentzian deconvolution of the O-H band Raman spectra we investigate the local structures created between water-water, water-alcohol, and alcohol-alcohol molecules, which are directly related to the solubility of the liquids. Comparison of the responses in bulk solutions and in solutions confined in the pores of the gelatin gel shows that for high ethanol concentrations solubility significantly increases with decrease of the pore sizes. [ABSTRACT FROM AUTHOR]

Using the empirical Brenner potential, we have calculated the structural and vibrational properties of single walled carbon nanotubes (SWNTs) with divacancies, based upon which their nonresonant Raman spectra have been calculated by the empirical bond polarizability model. It is found that the SWNT’s diameter will be changed by the divacancies, depending strongly on the tube’s chirality and the divacancy concentration. More importantly, it is found that the divacancy-induced Raman peaks lie out of the SWNT’s G-band and their positions depend on the tube’s chirality and the divacancy’s symmetry, which can be used to detect the divacancy experimentally. [ABSTRACT FROM AUTHOR]

Photoluminescence (PL) spectroscopy was used to determine lateral temperature distributions in AlGaN/GaN based devices. Results are compared to Raman thermography data and to thermal modeling to assess challenges in the determination of temperature in devices using PL analysis and corresponding solutions. In conjunction with Raman thermography, the vertical temperature distribution in the devices is determined and the thermal boundary resistance at the GaN/SiC interface extracted. [ABSTRACT FROM AUTHOR]

Hartree–Fock ab initio Raman spectra calculations and Raman spectroscopic measurements were carried out on amorphous selenium in order to identify the characteristic vibrational mode due to sigma bonds. Variations in measured peak intensity were observed as a consequence of band gap light illumination. Based on our previous theoretical investigations we originate these intensity variations from photoinduced covalent bond breaking. [ABSTRACT FROM AUTHOR]

We have investigated the plasmonic enhancement in the radiation field at various nanostructured multilayer devices that may be applied in surface enhanced Raman spectroscopy. We apply an image dipole method to describe the effect of surface morphology on the field enhancement in a quasistatic limit. In particular, we compare the performance of a nanostructured silver surface and a layered silver-gold hybrid device. It is found that localized surface plasmon states provide a high field enhancement in silver-gold hybrid devices, where symmetry breaking due to surface defects is a supporting factor. These results are compared to those obtained for multishell nanoparticles of spherical symmetry. Calculated enhancement factors are discussed on the background of recent experimental data. [ABSTRACT FROM AUTHOR]

High pressure Raman spectroscopy of NH3BH3–H2 mixtures up to 60 GPa reveals unusual pressure-induced complexation and intermolecular interactions. Stretching modes of H2 in the complex arise at 6.7 and 10 GPa, increasing in frequency with pressure of up to 60 GPa with different pressure coefficients, and at ∼40 GPa, the lower frequency mode approaches vibron frequency of bulk H2. Pressure-induced transformations in pure NH3BH3 studied up to 60 GPa reveal a disorder-order transition at 1 GPa (phase II) and further transitions at 5 (phase III) and 10 GPa (phase IV). The spectra of both pure NH3BH3 and the NH3BH3–H2 complex provide evidence for strengthened of the N–Hδ+...Hδ-–B dihydrogen bonding linkages up to 50 GPa, beyond which they weaken. The dihydrogen bonding breaks down due to interactions with H2 between 15 and 20 GPa in the NH3BH3–H2 complex. The behavior of the ν(NH3) modes in the NH3BH3–H2 complex indicates a dominant role of the NH3 functional group in the observed interactions. [ABSTRACT FROM AUTHOR]

High pressure Raman spectroscopy of NH3BH3–H2 mixtures up to 60 GPa reveals unusual pressure-induced complexation and intermolecular interactions. Stretching modes of H2 in the complex arise at 6.7 and 10 GPa, increasing in frequency with pressure of up to 60 GPa with different pressure coefficients, and at ∼40 GPa, the lower frequency mode approaches vibron frequency of bulk H2. Pressure-induced transformations in pure NH3BH3 studied up to 60 GPa reveal a disorder-order transition at 1 GPa (phase II) and further transitions at 5 (phase III) and 10 GPa (phase IV). The spectra of both pure NH3BH3 and the NH3BH3–H2 complex provide evidence for strengthened of the N–Hδ+...Hδ-–B dihydrogen bonding linkages up to 50 GPa, beyond which they weaken. The dihydrogen bonding breaks down due to interactions with H2 between 15 and 20 GPa in the NH3BH3–H2 complex. The behavior of the ν(NH3) modes in the NH3BH3–H2 complex indicates a dominant role of the NH3 functional group in the observed interactions. [ABSTRACT FROM AUTHOR]

The atomic-scale interactions of H atoms with hydrogenated amorphous carbon (a-C:H) films were identified using molecular dynamics (MD) simulations and experiments based on surface characterization tools. Realistic a-C:H films developed using MD simulations were impinged with H atoms with a kinetic energy corresponding to a temperature of 700 K. The specific chemical reactions of the H atoms with the a-C:H surface were identified through a detailed analysis of the MD trajectories. The MD simulations showed that hydrogenation occurs primarily at the sp2 sites and converts them to sp3-hybridized C atoms. Depending on the hybridization of the next-nearest neighbor, a dangling bond may or may not be created. The hydrogenation reaction is highly exothermic, >2.5 eV, and proceeds with a negligible activation energy barrier via a mechanism similar to Eley–Rideal. In certain cases hydrogenation may also cleave a C–C bond. The reaction events observed through MD simulations are consistent with the surface characterization of D-exposed a-C:H films using Raman spectroscopy, spectroscopic ellipsometry, and in situ attenuated total reflection Fourier-transform infrared spectroscopy. [ABSTRACT FROM AUTHOR]

The phase stability of YbVO4 under pressure has been investigated using synchrotron based angle dispersive x-ray diffraction and Raman spectroscopic techniques up to 34.5 and 26.5 GPa, respectively. The results indicate that the compound transforms from the ambient pressure zircon structure to the scheelite structure above 5.9 GPa with 11.8% volume discontinuity. The coexistence of the two phases is observed over a large pressure range. At 15.8 GPa, the (011) peak of the scheelite phase develops asymmetry, and the pattern at further high pressures could be fitted to a fergusonite-type monoclinic structure. On reducing the pressure, the fergusonite phase reverses back to the scheelite phase; the latter phase could be recovered as a metastable phase at ambient pressure. The refined structural parameters along with the equation of state are given for various phases of YbVO4. Changes in the vibrational properties across these transitions, particularly across the scheelite↔fergusonite transition, have been investigated using Raman spectroscopy. [ABSTRACT FROM AUTHOR]

The effects of high pressure (up to 9 GPa) on the thermal decomposition of ammonia borane, BH3NH3, were studied in situ by Raman spectroscopy in a diamond anvil cell. In contrast with the three-step decomposition at ambient pressure, thermolysis under pressure releases almost the entire hydrogen content of the molecule in two distinct steps. The residual of the first decomposition is polymeric aminoborane, (BH2NH2)x, which is also observed at ambient pressure. The residual after the second decomposition is unique to high pressure. Presumably it corresponds to a precursor to hexagonal BN where macromolecular fragments of planar hexagon layers formed by B and N atoms are terminated by H atoms. Increasing pressure increases the temperature of both decomposition steps. Due to the increased first decomposition temperature it becomes possible to observe a new high pressure, high temperature phase of BH3NH3 which may represent melting. [ABSTRACT FROM AUTHOR]

An anomalous solution behavior at the molecular scale was observed for macroscopically homogeneous mixtures of methanol and ethanol. Two-dimensional Raman correlation spectroscopy was used to elucidate the possible existence of microstructures formed in the mixture. The result suggests that separate methanol and ethanol clusters are formed without heterohydrogen bonding between different alcohol species. Supramolecular structures seem to be formed by the interaction of such clusters with each other through cohesion and dispersion forces, but not through direct hydrogen bonding connections. [ABSTRACT FROM AUTHOR]

A novel application of ionization-loss stimulated Raman spectroscopy (ILSRS) for monitoring the spectral features of four conformers of a gas phase flexible molecule is reported. The Raman spectral signatures of four conformers of 2-phenylethylamine are well matched by the results of density functional theory calculations, showing bands uniquely identifying the structures. The measurement of spectral signatures by ILSRS in an extended spectral range, with a conventional laser source, is instrumental in facilitating the unraveling of intra- and intermolecular interactions that are significant in biological structure and activity. [ABSTRACT FROM AUTHOR]

The behavior of cyclopentane with pressure has been investigated to 21.5 GPa using Raman spectroscopy. Various phases were observed with pressure which included liquid, two plastic, and one true crystalline phases of cyclopentane during compression and decompression sequences. Optimized molecular structure and Raman and IR vibrational spectra of the most stable puckered-ring conformation of the cyclopentane molecule were also computed using density functional theory methods. The theoretically calculated values as well as the experimentally determined pressure dependencies of spectral bands are in very good agreement with the low temperature measurements and previous mode assignments. The phase diagram of cyclopentane was analyzed with respect to pressure-induced alterations in Raman spectra across the phase boundaries. The various forms of “frozen-in” conformations in phase III are suggested to explain previous results related to existence of a “new” phase between plastic crystalline phase II and monoclinic phase III in solid cyclopentane. [ABSTRACT FROM AUTHOR]

Phase-selective growth of VO2 and V2O5 nanowires was realized via catalyst-free physical vapor deposition from bulk VO2 powder. Single nanowire Raman spectroscopy was used to analyze the distribution of the vanadium oxide phases within the reactor. VO2 (V2O5) nanowires were identified by characteristic peaks at 197, 224, and 620 cm-1 (149, 700, and 994 cm-1). Electron diffraction and polarization-dependent Raman spectra indicated that the growth directions of VO2 and V2O5 nanowires were [100] and [010]. Analysis of Raman spectra in two polarization configurations is sufficient to distinguish between low-index nanowire growth directions for the V2O5 phase. Single nanostructure Raman measurements thus provide a means to rapidly analyze the phase and growth direction of anisotropic nanostructures. [ABSTRACT FROM AUTHOR]

Epitaxial thin films of LaMnO3 were grown by pulsed laser deposition in identical deposition conditions but in situ annealed in different oxygen environments. All the films showed an insulator to metal transition. It also showed a magnetic order that correlates well with an insulator to metal behavior. The transition temperature critically depends on annealing oxygen pressure and increases with increasing oxygen content. It is observed that instead of strain, oxygen content plays a major role in deciding the transport properties. X-ray diffraction and Raman spectroscopy measurements revealed that the increasing oxygen content results in a decrease in unit cell volume along with a reduction in Jahn–Teller distortion. It is shown that the intensities of the two Jahn–Teller activated modes in Raman spectra are highly sensitive to the oxygen stoichiometry of the films and that the intensity ratio can be effectively used to characterize oxygen content in these films. [ABSTRACT FROM AUTHOR]

Raman and IR spectroscopies were applied for the investigation of optical phonons in relaxed InxAl1-xAs alloys grown by molecular-beam epitaxy on GaAs. From the analysis of Raman and IR data, the frequencies of longitudinal and transverse InAs- and AlAs-like optical phonons were derived in the whole composition range of the alloy (x=0–1). Analytical expressions are obtained for the frequency variation with In composition for the optical phonon modes, as well as the variations in their intensity and linewidth. Multiple-phonon Raman scattering up to the fourth order is observed under resonant conditions. [ABSTRACT FROM AUTHOR]