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     

Electronic interactions in two-dimensional polymers of the C60 fullerene

The electronic structure of tetragonal and rhombohedral polymers of the C₆₀ fullerene is investigated using x-ray emission spectroscopy. It is found that, compared to the C₆₀ molecular crystals, the formation of intermolecular covalent bonds in two-dimensional layers of the C₆₀ fullerene polymers leads to a broadening of the maxima in the CK _α x-ray emission spectra, a decrease in the density of high-energy states, and an increase in the width of the valence band of the polymer. The experimental data are interpreted by analyzing the results of the calculations performed within the density functional theory for the C₆₀ fullerene cage forming eight and twelve covalent bonds. It is shown that the electronic interactions between C₆₀ molecules in the polymerized layers are provided by two types of molecular orbitals located at energies 0.5–3.0 and ∼5.0 eV below the energy of the Fermi level.     

Microphotoluminescence of C<Subscript>60</Subscript> Fullerites Synthesized under a Pressure of 13 GPa and Temperatures of 770–2100 K

C₆₀ fullerite samples synthesized under a pressure of P = 13 GPa and temperatures of T_s = 770 ? 2100 K were studied by scanning microphotoluminescence (MPL) at room temperature. The MPL of cleaved chip surfaces indicates the presence of emitting areas with linear dimensions from 35 to 350 μ. A band at 700 nm, which is characteristic for linear and planar C₆₀ polymers, was revealed in all 3D-polymerized fullerites too. New bands at 1100?2300 nm are observed in PL spectra of substances synthesized at 870 ≤ T_s ≤ 1270 K. Separated areas of several optically active moieties responsible for luminescence in the range 1100?2300 nm were detected by MPL cartography. The origin of this band is tentatively attributed to traps located on C₆₀-oxygen and nitrogen inclusions associated with defects of the crystal lattice.     

Structural and spectroscopic properties of pressure-induced C70 polymers

70 by high pressure treatment at high temperature. Evidence for crosslinking is presented on the basis of X-ray diffraction pattern, infrared absorption, ultraviolet-visible absorption spectra. As was observed in C₆₀ polymers, C₇₀“polymerrdquo; is not soluble in toluene, and revert to conventional monomer crystals by heating to at ambient pressure. Received: 3 October 1996/Accepted: 10 December 1996     

Formation of metallofullerenes by laser ablation of externally doped fullerenes C60Mx (M=Sm, Pt and Ni)

Photofragmentation of metal fullerides C₆₀M_x (M=Sm, Pt and Ni) has been studied by excimer laser ablation–TOF mass spectrometry. Metallofullerenes of the type C_nM (n<60) have been observed in both the positive and negative ionic modes, with C₅₉M being the most prominent species. It is supposed that the metal atom is incorporated into the network of the fullerene cage to replace one carbon atom of the cage, forming substitutional metallofullerene. The occurrence of the C₅₉M, C₅₈M, C₅₇M clusters in the mass spectra is confirmed by the coincidence of the intensity distribution of the mass peaks with the isotopic abundance pattern calculated from the natural abundance of isotopes of C and M. Odd-numbered high-carbon clusters are observed in our laser ablation study of all the metal fullerides in the negative ion channel. The evolution of the mass spectra of these samples with laser irradiation shots indicates that the transformation process from an externally doped fullerene to the substitutionally doped fullerene involves the loss of metal carbide, MC. The structures of metallofullerenes C_2n+1M and C_2nM with even and odd total numbers of atoms respectively are discussed. Formation mechanisms with the participation of odd-numbered all-carbon fullerene clusters as intermediates are supposed. Received: 18 June 2001 / Accepted: 28 September 2001 / Published online: 2 May 2002     

Structural aspects of two-dimensional polymers: Li4C60, Na4C60 and tetragonal C60. Raman spectroscopy and X-ray diffraction

We present an analysis of three different two-dimensional polymers, tetragonal C₆₀, Li₄C₆₀, and Na₄C₆₀. Based on X-ray diffraction and Raman spectroscopy, we conclude that Li₄C₆₀ forms a tetragonal structure with intermolecular bonds formed by 2+2 cycloaddition, in the same way as for tetragonal C₆₀. Na₄C₆₀, on the other hand, forms a monoclinic structure with single C–C bonds between the molecules. Our Raman spectroscopy results can be interpreted in two ways: either the charge transfer to the C₆₀ molecules is the same in both doped compounds with four electrons/molecule or the electron charge transfer is smaller from the Li ions than from the Na ions.     

EPR evidence of the low temperature phase transition in C60

A standard EPR technique has been applied to perform temperature studies of polycrystalline samples of C₆₀ fullerene. A comparison of the three main parameters of EPR spectra obtained for a C₆₀ sample before and after (solvent free) purification has been made in temperatures from 4 to 300 K. When compared to the spectrum of the as-obtained (crude) sample the spectrum of the purified sample revealed considerable changes i.e. an increase in the EPR signal intensity and evidence of a phase transition at about 90 K. This transition is proved to be related to the two processes: freezing of the orientational motion of C₆₀ molecules and redistribution of the positive and negative charge observed as paramagnetic centres localized on C₆₀ molecules.     

Electron spin resonance study of bulk and nanosized La0.875Sr0.125MnO3

The structural, transport and electron spin resonance properties of bulk and nanosized La_0.875Sr_0.125MnO₃ prepared by a sol-gel method have been investigated. The bulk sample has an orthorhombic structure and a ferromagnetic insulating ground state. The ESR spectra indicate the coexistence of the ferromagnetic insulating and ferromagnetic metallic phases below T_C. In addition to a sharp peak in the vicinity of T_C, another sharp peak close to is clearly observed in the intensity of the spectra, which may be correlated with the structural transition and orbital ordering at this temperature. For the nanosized sample, a drastically different behavior is found. With a rhombohedral structure down to 70 K, the nanosized sample shows a ferromagnetic metallic ground state. The ESR studies reveal the coexistence of the paramagnetic and ferromagnetic resonance signals. The resonance intensity shows a broad peak around 200 K, which may be due to the wide ferromagnetic transition in the nanoparticle.     

Novel properties of nanoscale organic–inorganic systems and photonic crystals — conducting polymers in nanoscale periodic structures,microcavities and photonic crystals

Conducting polymer/C₆₀and C₆₀doped conducting polymer/C₆₀heterojunctions have been fabricated and found to exhibit remarkably enhanced photoresponse due to the highly effective photoinduced charge transfer at the interface. In conducting polymer/C₆₀alkali metal nanoscale composite systems, multiphase superconductivity has been clarified and explained by taking the coupling of nanoscale grains by Josephson junctions into consideration. As examples of intramolecular organic-inorganic combined systems, unique electrical and optical characteristics have been revealed in oligosilanylene oligophenylene polymers. Electroluminescence has been demonstrated in organic-inorganic junction devices such as conducting polymer/porous Si and conducting polymer/diamond junctions. Conducting, polymer-based nanoscale multilayer systems have been studied utilizing molecular self-assembly method and novel photosensitive characteristics have been revealed. \indent Novel optical and electrical properties of conducting polymers infiltrated in a photonic crystal, synthetic opal made of SiO₂spheres of several hundred nm in diameter, and also a conducting polymer replica have been revealed. A clear diffraction pattern was observed in a photonic crystal infiltrated with conducting polymers, and transmission spectra are dependent on various ambient conditions. Their photoluminescence (PL) spectra, spectral narrowing of PL and lasing characteristics at relatively low optical excitation have also been clarified. Novel conducting characteristics of conducting polymers in a photonic crystal that was prepared by pyrolysis of a polymer replica of opal have also been observed.     

Optical properties of fullerene and non-fullerene peapods

Single-wall carbon nanotubes (SWNTs) encapsulating fullerenes, so-called fullerene peapods, were synthesized in high yield by using diameter-selected nanotubes as pods. Transmission electron microscopy revealed high-density fullerene chains inside the nanotubes. X-ray-diffraction measurements indicate 85% filling for C₆₀ and 72% filling for C₇₀ molecules as a total yield. Interestingly, C₆₀ peas do not show any thermal expansion while C₇₀ peas show normal behavior. Room-temperature Raman spectra show one-dimensional photopolymerization of C₆₀ inside nanotubes by blue-laser irradiation, suggesting molecular rotation inside them. In C₇₀ peapods, no photopolymerization was observed but the relative Raman intensity of each peak is different from the C₇₀ 3D crystal. This is probably caused by mixing of two different crystal structures in C₇₀ peas. Furthermore, we synthesized Zn-diphenylporphyrin peapods. Optical absorption and Raman spectra suggest that the encapsulated molecules are deformed by interaction with the SWNT. Received: 12 November 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Thermal conductivity of pressure polymerized C60

60 polymerization in the temperature interval at pressures below by measurements of the time dependence of the thermal conductivity. It has been found at that the polymerization process at is slower than the reverse transformation from “polymeric” to “monomeric” phase at . The thermal conductivity of polymerized C₆₀ was measured in the temperature range and found to increase with increasing temperature, which reflects strong phonon scattering. Both the presence of non-bonded C₆₀ molecules and a high degree of structural disorder in the crystalline lattice of the polymeric phase might be responsible for the behaviour of . The results for are qualitatively similar to those reported previously for C₆₀ polymerized at higher , but an order of magnitude smaller. Received: 20 September 1996/Accepted: 11 November 1996     

Polymeric sheets in Mg4C60

We present preliminary results on the preparation and structure of Mg₄C₆₀, a new fulleride polymer. A series of Mg_xC₆₀ compositions (0<x<6) were prepared by solid state reaction. While most samples were multiphase, a single phase material was obtained at the nominal composition Mg₄C₆₀. The X-ray diffraction pattern of Mg₄C₆₀ was successfully indexed and fitted to a rhombohedral structure based on two-dimensional polymeric sheets of C₆₀ ions. This result extends the family of fulleride polymers to the salts of multiply charged cations and thus opens a new direction in this field.     

On interface dipole layers between C60 and Ag or Au

C₆₀ layers on polycrystalline Ag and Au are studied by photoelectron spectroscopy. At these metal/C₆₀ interfaces an electron transfer occurs from the metal to the lowest unoccupied orbital of C₆₀. We found in the case of the polycrystalline Ag/C₆₀ interface a dipolar layer with its associated electric field in the direction corresponding to the charge transfer, so pointing from the substrate to the adsorbent. Yet, at the Au/C₆₀ interface we observed an overall electric field pointing from C₆₀ towards the metal. We discuss our observations in terms of charge transfer, screening and hybridization effects and propose the occurrence of a hybridization mechanism similar to back-bonding at the Au/C₆₀ interface. We show that the alignment of energy levels at the metal/C₆₀ interface cannot simply be deduced using the metal workfunction and the frontier orbitals of C₆₀, including screening effects, since hybridization effects may strongly alter the interfacial energy level structure. Our experimental findings on the polycrystalline metal/C₆₀ interfaces indicate an at-most weak dependence of the Fermi level of the C₆₀ overlayer on the workfunction of the polycrystalline metal substrate. These interfaces are found in donor–acceptor-based organic photovoltaic devices and our results may help to understand the electrical characteristics of these devices. Received: 26 September 2001 / Accepted: 15 January 2002 / Published online: 3 June 2002     

Resonance Raman excitation and electronic structure of the single bonded dimers (C ¯60)2 and (C 59N)2

Raman spectra are presented for the single bonded dimeric fullerene (C ₆₀ ^- ) ₂ and compared to optical spectra and Raman spectra of the isostructural and isoelectronic heterofullerene (C₅₉N)₂. The spectra of both materials exhibit strong correlations with respect to splitting, line position, and line intensity. This holds for non resonant excitation with blue and green lasers as well as for the strong resonances observed with red lasers. The latter observation is consistent with a downshift for the electronic transition energies as compared to C₆₀. The absorption edge of thin films of (C₅₉N)₂ was found at 1.4 eV. The three intercage modes were observed at 82, 103, and 111, and at 88, 98, and 106 cm^-1 for (C₅₉N)₂ and (C ₆₀ ^- ) ₂ , respectively. A surprising difference was found for the position of the pentagonal pinch modes in the two materials as they were observed at 1461 and at 1451 cm^-1, for (C₅₉N)₂ and (C ₆₀ ^- ) ₂ , respectively. This is interpreted as a consequence of some characteristic differences in the electronic structure of the two compounds. Received 25 January 2000 and Received in final form 10 April 2000     

Study of oxygen-C 60 compound formation by NEXAFS and RIXS

The interaction of oxygen with C₆₀ molecules was studied on a C₆₀ film which had been exposed simultaneously to oxygen and UV-light for 190 hours, producing an approximately C₆₀O₁ stoichiometry in the bulk of the sample. C K-edge and O K-edge NEXAFS (using total fluorescence yield detection) and resonant X-ray inelastic scattering (RIXS) spectra from the sample film were measured and the C K-edge data were compared to the spectra from pristine C₆₀ as reference. The C K-edge absorption and emission spectral profiles of the oxygen-doped sample are similar to those of the C₆₀ reference, suggesting that cage breaking of C₆₀ under these conditions, if any, is negligible. However, the redistribution of intensities in the spectra indicates changes in the occupancies of different molecular orbitals, possibly due to changes in electron density upon reaction. Similarities of the O K-edge soft X-ray emission (SXES) spectra to several small oxygen-containing molecules is being discussed in terms of bonding models. Received 4 December 2000     

Polymerization of solid C<Subscript>60</Subscript> under C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> cluster ion bombardment

The structure transformation occurring in fullerene film under bombardment by 50 keV C₆₀⁺ cluster ions is reported. The Raman spectra of the irradiated C₆₀ films reveal a new peak rising at 1458 cm⁻¹ with an increase in the ion fluence. This feature of the Raman spectra suggests linear polymerization of solid C₆₀ induced by the cluster ion impacts. The aligned C₆₀ polymeric chains composing about 5–10 fullerene molecules have been distinguished on the film surface after the high-fluence irradiation using atomic force microscopy (AFM). The surface profiling analysis of the irradiated films has revealed pronounced sputtering during the treatment. The obtained results indicate that the C₆₀ polymerization occurs in a deep layer situated more than 40 nm below the film surface. The deep location of the C₆₀ polymeric phase indirectly confirms the dominant role of shock waves in the detected C₆₀ phase transformation.     

A Brillouin study of the temperature-dependence of the acoustic modes across the insulator-metal transitions in V2O3 and Cr-doped V2O3

Brillouin scattering studies have been carried out on high-quality single crystals of undoped and 0.9% Cr-doped V₂O₃. The observed modes in both the samples at ∼12 and ∼60 GHz are associated with the surface Rayleigh wave (SRW) and bulk acoustic wave (BAW), respectively. In the undoped sample, the mode frequencies of the SRW and BAW modes decrease as the temperature is lowered from room temperature to the insulator-metal transition temperature (T_IM=T_N=∼130 K). Below the transition, the modes show hardening. In the doped sample, the SRW mode shows a similar temperature-dependence as the undoped one, but the BAW mode shows hardening from room temperature down to the lowest temperature (50 K). This is the first measurement of the sound velocity below T_IM in the V₂O₃ system. The softening of the SRW frequency from 330 K to T_IM can be qualitatively understood on the basis of the temperature-dependence of C₄₄, which, in turn, is related to the orbital fluctuations in the paramagnetic metallic phase. The hardening of the mode frequencies below T_IM suggests that C₄₄ must increase in the antiferromagnetic insulating phase, possibly due to the orbital ordering.     

Doping and photoelectric properties of C60 films prepared by ionized cluster beam deposition

60 films by means of ionized cluster beam (ICB) deposition. X-ray diffraction (XRD) measurement showed the C₆₀ films to be polycrystalline. The films show negative resistance–temperature coefficients, and their room-temperature resistivity is greater than 10² Ω cm. The films were implanted with 80-keV phosphorus, BBr₃, Ar, and He ions, under doses ranging up to 10¹⁶ cm^-2. The resistivity of the implanted films decreases with increasing doses. n-type electrical conduction was observed for phosphorus-implanted C₆₀ films. The interaction of impinging ions with C₆₀ clusters was found to force the C₆₀ molecules to disintegrate and the films to amorphize. p-type conduction was observed for the C₆₀ films doped with aluminum by simultaneously sputtering aluminum during deposition. C₆₀/Si structures show heterojunction characteristics that can be influenced by light illumination. The photoelectric properties of the films were found to be improved by doping with aluminum. Received: 12 January 1998/Accepted: 24 March 1998     

Spectroscopic characterization of pressure modified C60

60 are reported. The material associated with the mixture of rhombohedral and tetragonal phases was synthesized under pressure of when treatment temperature was only a little lower than the high-temperature limit of C₆₀ stability. The substance exhibits very rich infrared and Raman spectra as well as luminescence spectra of an unusual shape. They show that vibrational transitions in the prepared carbon architecture substantially deviate from icosahedral symmetry of buckyballs and exhibit a similarity with lattice phonons in graphite. It may originate from mixing of C₆₀ modes and vibrations of a layer structure on deformed and weakly bound fullerene molecules. The luminescence spectra reveal three distinct electronic states located below . One of them responsible for the emission peak at is very characteristic for the pressure modified fullerene. The data should be useful for the accurate determination of structural changes in C₆₀ induced by pressure. Received: 6 September 1996/Accepted: 10 October 1996     

Phase transitions in hydrofullerene C<Subscript>60</Subscript>H<Subscript>36</Subscript> studied by luminescence and Raman spectroscopy at pressures up to 12 GPa

The effect of hydrostatic pressure on the photoluminescence and Raman spectra of hydrofullerene C₆₀H₃₆ was investigated for pressures up to 12 GPa at room temperature. The samples were synthesized by means of high-pressure hydrogenation. The pressure coefficients of the phonon modes were found to be positive and demonstrate singularities at ～0.7 and ～6 GPa. The pressure shift of the luminescence spectrum is unusually small and increases slightly at P≥6 GPa. All observed features are reversible with pressure, and C₆₀H₃₆ is stable in the pressure region investigated.