Raman Spectroscopic Studies of Pressure-Induced Phase Transitions on 1-Dodecene

Raman spectroscopic features of 1-dodecene are studied in a moissanite anvil cell up to 3.0 GPa at 21℃. Our data indicate that 1-dodecene is chemically stable under the experimental condition because no new Raman peaks can be observed. However, two significant discontinuities in the plots of Raman shift versus pressure indicate two phase transitions of 1-dodecene. One is liquid~olid transition at pressure of about 500 MPa, the other is solid-solid phase transition at pressure from 1300 to 1550 MPa. The latter is considered to be related to the orientational change of the plane structure of ethylene. A rudimentary phase diagrams for 1-dodecene, n-pentane, n-hexane are proposed based on the results and previous data.     

Intermediate frequency modes in Raman spectra of Ar+‐irradiated single‐wall carbon nanotubes

We study the effect of Ar⁺ irradiation on the intermediate frequency modes (IFM) in Raman spectra of single‐wall carbon nanotubes. We observe new features in the intermediate frequency region from 386 to 635 cm^–1 as the defect concentration increases, whereas at the same time there is a decrease of other IFM modes. After annealing in vacuum, the IFM modes recover and become similar to those of the nanotubes before irradiation. We interpret the new features in the Raman spectra as originating from the phonon density of states that becomes visible in the Raman process due to the presence of defects. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A Raman study of polymerised C60

60 are reported. Although prepared according to different routes the Raman spectra of the two polymeric phases of C₆₀ show a quantitative agreement with respect to mode positions and intensity. We conclude from this that both materials have the same structure at least in the short range order, i.e. the same type of bonding and co-ordination between neighbouring C₆₀ molecules. An investigation of the time dependence of the thermal decomposition of high pressure polymerised C₆₀ is also presented. The rate of decomposition of the polymeric phase is found to be multi-exponential at all temperatures investigated. From an Arrhenius-type analysis of the short time data and the long time data, respectively, the activation energy for thermal dissociation of polymeric bonds was found to increase with time. Received: 20 September 1996/Accepted: 11 November 1996     

Stimulated electronic Raman scattering in In vapor

High power density electron beams offer new opportunities for studies of epitaxial growth of semiconductor materials. Assuming that the mechanism of epitaxial growth can be understood as a surface melting followed by supercooling regrowth, the heat flow equation has been applied to calculate the temperature reached after an electron beam pulse of power density between 0.5–2 J/cm². Comparison with laser annealing is made.     

Phase Transition in CCl4 under Pressure: a Raman Spectroscopic Study

High-pressure Raman studies at room temperature are performed on CCl₄ up to 13GPa. The Raman bands of the internal modes (v₂, v₄ and v₁) show entirely positive pressure dependence. The slopes dω/dP of the internal modes exhibit two sudden changes at 0.73GPa and 7.13GPa, respectively. A new lower frequency mode (225cm^-1) appears at 3.03GPa, and the splitting of v₂, ν₃ and v₄ occurs at about 7.13GPa. Moreover, Raman spectra of Fermiresonance show that the relative position of the v₁ + v₄ combination and the ν₃ fundamental firstly interchanges corresponding to that at ambient pressure, then the v₁ +v₄ combination disappears in the gradual process of compression. It is indicated that the pressure-induced phase transition from CCl₄ II to CCl₄ III occurs at 0.73GPa, and CCl₄ III undergoes a transition to CCl₄ IV below 3.03GPa. Further CCl₄ IV transforms in a new high-pressure phase at about 7.13GPa, and the symmetry of the new high-pressure phase is lower than that of CCl₄ IV. All the transitions are reversible during decompression.     

Simulation of composition modification in ZnSe by nanosecond radiation of excimer laser

A numerical simulation of the composition modification induced in ZnSe by nanosecond irradiation of the KrF excimer laser (λ = 248 nm, τ = 20 ns) has been carried out. Intensive evaporation of components has shown to results in the material surface cooling and forming a nonmonotone temperature profile with maximum temperature in semiconductor volume at the distance of ∼6 nm from the surface. As a result of evaporation and diffusion of components formation of the near-surface layer with nonstoichiometric composition takes place and enrichment of selenium reaches maximum value not on the surface, but in the semiconductor volume.     

Simulation of dynamics of phase transitions in CdTe by pulsed laser irradiation

Numerical simulation of melting and solidification processes induced in CdTe by nanosecond radiation of ruby laser (λ = 694 nm, τ = 20 and 80 ns) and KrF excimer laser (λ = 248 nm, τ = 20 ns) taking into account components diffusion in melt and their evaporation from the surface has been carried out. Cd atoms evaporation has shown to essentially affect the dynamics of phase transitions in the near-surface region. Thus, in the case of the influence of ruby laser irradiation intensive surface cooling results in the formation of nonmonotone temperature profile with maximum temperature in semiconductor volume at the distance of ∼20 nm from the surface. The melt formed under the surface extends both to the surface and to the semiconductor volume as well. As a result of cadmium telluride components evaporation and diffusion in the melt the near-surface region is enriched with tellurium. The obtained melting threshold value of irradiation energy density is in a reasonable agreement with experimental data.     

Raman Spectroscopy of Irradiation Effect in Three Carbon Allotropes Induced by Low Energy B Ions

Irradiation effect in three carbon allotropes C60, diamond and highly oriented pyrolytic graphite （HOPG） induced by 170keV B ions, mainly including the process of the damage creation, is investigated by means of Raman spectroscopy technique. The differences on irradiation sensitivity and structural stability for C60, HOPG and diamond are compared. The analysis results indicate that C60 is the most sensitive for B ions irradiation, diamond is the second one and the structure of HOPG is cross sections σ of C60, diamond and HOPG deduced from 1.31 × 10^-15 cm^2, respectively. the most stable under B ion irradiation. The damage the Raman spectra are 7.78 × 10^-15, 6.38 × 10^-15 and1.31 x 10-15 cm^2, respectively.     

A double-temperature-gradient technique for the growth of single-crystal fullerites from the vapor phase

Fullerite single crystals were prepared by a sublimation-condensation method in a closed evacuated glass tube situated in a double-temperature-gradient furnace. Crystals of various size and up to 9 mg weight with well expressed smooth and shiny faces were obtained. X-ray analysis, interfacial angle measurements and observed morphological habits of selected crystals of C₆₀ confirm the theoretically predicted and experimentally well established fcc structure at room temperature with two types of morphological faces, namely {111} and {100}. A strong tendency to twinning was observed. In the case of C₇₀ crystals, a pure fcc structure was observed. Information on growth kinetics and on instability versus exposure to air and light were obtained from surface studies. Characteristic changes in a thin surface layer were observed when crystals were exposed to air and light. A new phase of C₆₀ stabilized by oxygen was characterized.     

Effect of ZnS shell on the Raman spectra from CdSe nanorods

We investigated the influence of an epitaxially grown ZnS shell on the phonon spectra of CdSe nanorods of different sizes. The CdSe related Raman peaks shift with addition of a ZnS shell. The longitudinal optical phonon shifts slightly due to strain and the low‐energy shoulder shifts stronger, which can be explained within a model for surface optical phonons. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Vibrational analysis of IR reflection-transmission from single crystal C60

We represent results of IR reflectivity and transmission measurements in the spectral range from 50 to 5000 cm^–1 for crystallographic {111} and {100} planes of C₆₀ single crystals between 80 K and 460 K. The spectra turned out to be highly anisotropic due to differences in geometric resonances. The geometries used allowed detailed simultaneous investigation of the four infrared activeF _1u fundamental modes together with some weak silent modes and the whole set of second- and third-order combination modes from an analysis of the reflection-transmission response. Photopolymerization is observed on the surface of the crystals after illumination in argon atmosphere. The orientational phase transition at 260 K is accompanied by a dramatic jump in the line widths within a fraction of a degree. This result is explained by a broadening mechanism due to collisions with librons and paralibrons for the low temperature phase and for the high temperature phase, respectively.     

The composition dependence and new assignment of the Raman spectrum in lithium tantalate

The Raman scattering spectra of lithium tantalate crystals with different compositions were investigated. The comparison of the Raman data obtained for the congruent and the near-stoichiometric crystals reveals some differences in the shape and the number of Raman peaks, which lead to a new assignment of the long-wavelength optical phonons. And quantitative relationships between the linewidth of Raman peaks (142 cm⁻¹ for E-phonon and 861 cm⁻¹ for A₁-phonon) and the crystal composition were firstly presented. Two local Raman lines, 278 and 750 cm⁻¹, were found for the congruent crystals and attributed to the intrinsic defects, Li vacancy and anti-site Ta ion, respectively.     

Crystal field and molecular structure in solid C60

The crystal field in the orientationally disordered phase of C₉₀-fullerite is derived from an intermolecular potential model, which takes into account the geometric difference between double bonds and single bonds. The molecules are modelled as rigid bodies, atoms and single bonds are treated as single interaction centers, while double bonds are described by a distribution of interaction centers along the bond. The crystal field is expanded in terms of cubic rotator functions. The calculated expansion coefficients are compared with empirical values derived from diffraction data. The angular dependence of the crystal field, resulting from an anticlockwise rotation of the molecule around the [111] axis, exhibits an absolute and a secondary minimum at angles of 98° and 38° respectively. The self interaction of the molecule in a deformable lattice is investigated.     

Temperature dependence of infrared and Raman modes in polymeric RbC60

Temperature dependence of the intra-molecular vibrational modes of C₆₀ in the quasi-1D polymeric RbC₆₀, across the low temperature transition at ∼50 K, has been probed through infrared (IR) and Raman spectroscopies. With the lowering of temperature, the split IR modes of RbC₆₀ are seen to harden but below 50 K a small but definitive signature of an anomalous softening is observed. In addition, the background IR transmission shows an increase below 50 K with the opening of a well defined gap in the electronic spectrum. The implications of these results, along with those of Raman measurements, are discussed in terms of the interaction of intra-molecular phonons with electrons and spin excitations in the system.     

High-temperature conductivity study on single-crystal C60

We report about dc, ac (100Hzv100kHz) and contactless microwave (10 GHz) conductivity studies on C₆₀ crystalline bulk material from room temperature to 850 K. The high temperature regime is governed by an activated behavior with a frequency and sample independent activation energy of about 0.9 eV. The low temperature regime exhibits a frequency dependent and weakly temperature dependent conductivity due to extrinsic properties.Anomalies in the heating curves of virgin samples (dynamical vacuum conditions) in the temperature ranges 560 K and 740 K are ascribed to the desorption of oxygen.     

Thermal conductivity of C60 and C70 crystals

We have performed thermal conductivity measurements on C₆₀ and C₇₀ crystals grown by sublimation. For single crystal C₆₀, the thermal conductivity k is 0.4 W/m K at room temperature and is nearly temperature independent down to 260K. We observed a sharp orientational phase transition at 260K, indicated by a 25% jump in k. Below 90K, k is time dependent, which manifests itself as a shoulder-like structure at 85K. The temperature and time dependence of k below 260K can be described by a simple model which accounts for the thermally activated hopping of C₆₀ molecules between two nearly degenerate orientations, separated by an energy barrier of 240 meV. It is found that solvents have a strong influence on the physical properties of C₇₀ crystals. For solvent-free C₇₀ crystal, k is about constant above 300K. There is a broad first-order phase transition in k at 300K with a 25% jump. We associate this transition with the aligning of the fivefold axes of the C₇₀ molecules along the c-axis of the hexagonal lattice. Upon further cooling, k increases and is time independent.     

Radial breathing modes of single-walled carbon nanotubes in resonance Raman spectra at high temperature and their chiral index assignment

Radial breathing modes (RBMs) in resonance Raman spectra from single-walled carbon nanotubes (SWCNTs) on a SiO₂/Si (0 0 1) substrate are studied between 25 and 720 °C. A change in the relative intensity of each RBM peak with temperature is observed, which originates from the temperature dependence of the resonance condition of nanotubes. For 25 °C, each RBM peak is reasonably assigned on the basis of data in the literature [J. Maultzsch, H. Telg, S. Reich, F. Hennrich, C. Thomsen, Phys. Rev. B 72 (2005) 205438]. By taking into account the temperature-dependent behavior of the relative intensity of the RBM peaks, each RBM peak is successfully assigned even for 720 °C. It is found that most of the observed RBM peaks for a laser excitation energy of E_exc = 1.96 eV are from chiral SWCNTs. These results make it possible to discuss further details of the chirality-dependent growth behavior observed for in situ Raman spectroscopy.     

Preparation and crystal structure of C60S16

A new fullerene-containing van der Waals-compound, C₆₀S₁₆, has been synthesized and its crystal structure determined from single-crystal X-ray diffraction data collected at room temperature. The compound is monoclinic, space group C 2/c with a=20.867(4) Å, b=21.062(4) Å, c=10.508(2) Å, =111.25(7)° and four formula units per cell. The C₆₀ molecules form a three-dimensional framework with one-dimensional channels along c which contain crown-shaped S₈ rings. The structure has been determined by direct methods and has been refined to atomic resolution on the C₆₀ molecule. The two independent C-C bond distances, averaged under the idealized point symmetry of the free C₆₀ molecule, amount to 1.340(8) Å and 1.448(8) Å, corresponding to a bond alternation as large as 0.108(8) Å. The bond lengths are compared with the results of theoretical calculations of the molecular structure of C₆₀ as well as with bond lengths from various experimental sources.