Photon emission from adsorbed C60 molecules with sub-nanometer lateral resolution

We present the first experimental demonstration of spatially resolved photon emission of individual molecules on a surface. A scanning tunneling microscope (STM) was used as a local electron source to excite photon emission from hexagonal arrays of C₆₀ molecules on Au(110) surfaces. Specifically, we show that in maps of photon emission intensities, C₆₀ fullerenes appear as arrays of individual light emitters 4 Å in diameter and separated by 10 Å. Comparison with simultaneously recorded STM images reveals, that most intense emission is detected when the STM tip is centered above a molecule. The results demonstrate the highest spatial resolution of light emission to date using a scanning probe technique.     

SiC bonding in ( C 60 ) n Si m clusters

This paper deals with a new type of SiC bonding where silicon atom seems to bridge C₆₀ molecules. We have studied films obtained by deposition of (C₆₀)_nSi_m clusters prepared in a laser vaporization source. Prior deposition, free ionized clusters were studied in a time-of-flight mass spectrometer. Mixed clusters (C₆₀)_nSi_m were clearly observed. Abundance and photofragmentation mass spectroscopies revealed the relatively high stability of the (C₆₀)_nSi _n ⁺ , (C₆₀)_nSi _{n - 1} ⁺ and (C₆₀)_nSi _{n - 2} ⁺ species. This observation is in favor of the arrangement of these complexes as polymers where the C₆₀ cages may be bridged by a silicon atom. Free neutral clusters are then deposited onto substrate making up a nanogranular thin film (≃ 100 nm). The film is probed by Auger and X-ray photoemission spectroscopies, but above all by surface enhanced Raman scattering. The results suggest an unusual chemical bonding between silicon and carbon and the environment of the silicon atom is expected to be totally different from the sp³ lattice: ten or twelve carbon neighbors might surround silicon atom. The bonding is discussed to the light of the so-called fullerene polymerization as observed for pure fullerite upon laser irradiation. This opens a new route for bridging C₆₀ molecules together with an appreciable energy bonding, since the usual van der Waals bonding in fullerite could be replaced by an ionocovalent bond. Such an assumption must be checked in the future by XAS and EXAFS experiments. Received 15 November 2000     

Molecular fusion within fullerene clusters induced by femtosecond laser excitation

Molecular fusion is induced in clusters of fullerene molecules on excitation with fs laser pulses. The dependence of the mass distributions of the fused products on the initial cluster distribution are studied and results for (C₆₀)_N and (C₇₀)_N clusters are compared. The fused products decay by emitting C₂ molecules and the fragmentation spectrum is used to determine the initial excitation energy of the fused species. The threshold excitation energy needed to induce fusion is consistent with the energetic thresholds for molecular fusion of fullerenes determined previously in single collision experiments.     

Modelling chemical kinetics of small clusters after nanosecond laser ablation

Nanoclusters of various materials have recently been obtained by laser ablation. Strong evaporation of a condensed phase caused by laser irradiation is well known to generate an overcooled vapour. Further expansion thereof increases the oversaturation degree and facilitates homogeneous nucleation and cluster growth. To investigate homogeneous nucleation at very high expansion rates attained at nanosecond laser ablation, kinetic equations are applied describing all the possible gas-phase chemical reactions of dissociation and coalescing between small clusters. Additional cooling due to thermal emission by clusters is taken into account. Twenty smallest carbon molecules are considered. The model is applied to nanosecond laser ablation of graphite in vacuum. The resulted vapour molecular composition is characterised by dominating molecules C₃ and C₅ and an exponential drop of heavier clusters concentrations with their mass. The growth of heavier clusters is controlled by the balance between liberating the latent heat of their formation and the energy losses by expansion and thermal emission.     

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     

Determination of C60/C70 ratios in fullerene mixtures and film characterization by scanning tunneling microscopy

Fullerene powder mixtures with different C₆₀/C₇₀ ratios have been analyzed by a variety of techniques, and results have been compared. The fullerence mixtures have been characterized as solutions in n-hexane by high-pressure liquid chromatography (HPLC) and UV-VIS spectroscopy. Thin films of fullerenes on Au(111) have been prepared from the mixtures by sublimation. The sublimation process has been studied by simultaneous thermogravimetric and differential thermal analyses. Thin fullerene films on Au(111) have been investigated by scanning tunneling microscopy (STM). The STM images show primarily two types of ballshaped molecules arranged in a lattice with hexagonal symmetry (fcc(111) face, nearest neighbour distance: 1 nm). The two species differ in diameter. STM images of films made of mixtures of different C₆₀/C₇₀ ratios show that C₇₀ molecules display a larger apparent diameter (0.8 nm) and corrugation than C₆₀ molecules (0.7 nm). The C₆₀/C₇₀ ratios obtained by counting the corresponding molecular species in the STM images of the thin films are compared to the C₆₀/C₇₀ ratios determined by HPLC on hexane solutions of the mixtures. The observed differences might be explained by different rates of sublimation for the two species. The STM images reveal film defects (vacancies and boundaries) and dynamic processes (displacement of C₇₀ molecules and vacancies). In films prepared to have a C₆₀ coverage of less than one monolayer, stable structural units of the C₆₀(111) surface consisting of three or seven C₆₀ molecules are revealed by STM. Occasionally, substructure within individual fullerene molecules is observed.     

A new approach to analyse H⊗(2h⊕g) Jahn-Teller system for C60

It is now well-known that electron (hole)-vibron coupling and hence Jahn-Teller (JT) effect is important understanding the properties of C₆₀ and related molecules. In this paper, we study H(2) coupling case to find the potential energy surfaces for the positively charged C₆₀ molecule due to distortion. The H(2) Jahn-Teller system is of particular importance as this will be the JT effect displayed by C₆₀ molecules removed with an electron. C₆₀ ⁺ is obtained by removing one electron from fivefold degenerate H_u highest occupied molecular orbital (HOMO) and a hole in HOMO interacts with the vibrational modes of C₆₀ and symmetry is broken. We apply the method of symmetry breaking mechanism to obtain expressions for the potential energy surface. Received 27 December 1999 and Received in final form 15 May 2000     

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     

Giant fullerenes formed on C60 films irradiated with electrons field-emitted from scanning tunneling microscope tips

It has been found that spherical large clusters of carbon atoms are formed by irradiation of crystalline C₆₀ films grown on Si(1 1 1)-(7 × 7) surfaces with electrons field-emitted from a scanning tunneling microscope probe tip. The size distribution of the clusters deduced from surface profile measurements suggests that the dominant clusters were not necessarily C_60n (n = 2-4) expected from the simple fusion of C₆₀ molecules. It was proposed that electronic excitations of C₆₀ molecules caused the fragment and coalescence of the molecules to form the giant fullerenes as in the photo-induced similar effects.     

Atomic force microscopy of C60/C70 single-crystal fullerenes under ethanol

C₆₀/C₇₀ crystal surfaces were imaged by atomic force microscopy under ethanol with resolution of single molecules. Spherical and elongated elliptical fullerenes can be distinguished corresponding most likely with C₆₀, respectively C₇₀. Determination of the maximum diameter for a large number of molecules confirms the presence of two species of fullerenes, one with 9.4 Å, the other with 11.2 Å. The measured ratio C₆₀:C₇₀ is 81:19 which resembles the spectroscopical data. The molecules are arranged either in hexagonal (hcp) or cubic (fcc) packing, in some areas the two arrangements alternate within a few nm. Elongated fullerenes apparently prefer the hexagonal packing.     

Bucky-corn: van der Waals composite of carbon nanotube coated by fullerenes

ABSTRACT

Can a C₆₀ layer cover a surface of single-wall carbon nanotube (SWCNT) forming an exohedral pure-carbon hybrid with only van der Waals interactions? The aim of the present paper is to address this question and to demonstrate that the fullerene shell layer in such a bucky-corn structure can be stable. Theoretical study of the structure, stability and electronic properties of bucky-corn hybrids is reported for the shell of C₆₀ and C₇₀ molecules on an individual SWCNT, C₆₀ dimers on an individual SWCNT as well as C₆₀ molecules on SWNT bundles. The geometry and total energies of the bucky-corn hybrids were calculated by the molecular dynamics method, while the density functional theory method was used to simulate the electronic band structures.     

Molecular beam deflection experiments on mixed clusters

Gas phase Ti-C₆₀ clusters are studied by molecular beam electric deflection. The permanent dipole moment of the TiC₆₀ molecule is determined. It is equal to 8.1±1.5 D. This dipole is due to a transfer of electron from the transition metal atom to the C₆₀ cage. No dipole is observed for Ti(C₆₀)₂ molecules. This is in agreement with the symmetrical dumbbell-like structure that has been previously proposed. Received 22 November 2000     

Formation of fullerene clusters in carbon disulfide: Data on small-angle neutron scattering and molecular dynamics

Fullerene solutions in carbon disulfide are studied by small-angle neutron scattering (SANS). In addition to earlier experiments on the given system, the range of measured transmitted impulses is extended and the influence of solution preparation methods on C₆₀ cluster formation in these solutions is studied. It is shown that the formation of large C₆₀ clusters (with a size of about 10 nm) is due to nonequilibrium methods of solution preparation. For nonequilibrium dissolution, there is a 10% excess of the observed fullerene size in the solution over the calculated value. It has been established by simulation of the C₆₀/CS₂ interface by molecular dymanics methods that inclusion of how solvent molecules are organized on the C₆₀ surface leads to a decrease in the fullerene size in the solution, observed by using SANS. In this paper, the effect of excess R _g is explained by the presence of small clusters in the solution (approximately 10% of dissolved C₆₀ molecules). It is discovered that there is a time variation in the concentration of the saturated solution. The explanation of this effect using a model of formation and sedimentation of large clusters (with a size of 100 nm or more) is proposed.     

Electronic structure and spectra of N-methylfullerenepyrrolidine

A quantum-chemical analysis of the donor-acceptor properties of a C₆₀ + dimethylenemethylamine binary system is performed. It is shown that the term of the intermolecular interaction is two-well, because of which the optimization of the system structure at the initial distances between the molecules of 0.21 nm or smaller leads to the formation of N-methylfullerenepyrrolidine C₆₀. At initial distances exceeding 0.25 nm, a weakly bound charge transfer complex with almost complete retention of the properties of the individual molecules is formed. The low-temperature emission and absorption vibronic spectra of N-methylfullerenepyrrolidine C₆₀ in the crystalline toluene matrix are studied experimentally. It is found that the absorption spectra of the fulleroid and pure fullerene in the region corresponding to the excitation of the lowest electronic states are generally similar. The difference observed between the low-frequency spectra agrees completely with the quantum-chemical analysis performed.     

Radiative cooling of fullerene anions in a storage ring

Thermionic emission from hot fullerene anions, C_N ^-, has been measured in an electrostatic storage ring for even N values from 36 to 96. The decay is quenched by radiative cooling and hence the observations give information on the intensity of thermal radiation from fullerenes. The experiments are analysed by comparison with a simulation which includes the quantisation of photon energy and the statistics of emission. Experiments with heating of the molecules with a laser beam confirm the interpretation of the observations in terms of radiative cooling and give an independent estimate of the cooling rate for C₆₀ ^-. The measured cooling rates agree in general within a factor of two with the prediction from a classical dielectric model of a thermal radiation intensity of ∼ 300 eV/s for C₆₀ at 1 400 K, scaling approximately with the 6th power of the temperature and with the number of atoms in the molecule. Received 12 March 2001 and Received in final form 12 June 2001     

Structures and energetics of carbon bridged C 60 clusters

The structures and energetics of carbon bridged C₆₀ clusters (C ₆₀ ) _n C_m have been studied by simulated annealing technique within the tight-binding molecular-dynamics. The “sp² addition” ball-and-chain dimers exhibit odd-even alternations over the number of chain atoms, with the dimers containing even chain atoms more stable against dissociation than their immediate neighbors containing odd chain atoms. In addition to the usual “sp² addition” dimers, a pentagon-linked C₁₂₁ isomer and a hexagon-linked C₁₂₂ isomer are also found to be stable. Based on our tight-binding calculations, trimers and larger clusters can be simply regarded as being made up of independent or weakly interacting dimers, if the C-C₆₀ joints on a single cage are not too close to each other. Large C₆₀ clusters connected by chains each containing only one or two carbon atoms have similar stability to that of constituent dimers, indicating the possibility to form stable C₆₀-carbon polymers. Received 17 January 2001 and Received in final form 26 February 2001     

Chemical adsorption of C60 on diamond (100)(2×1) surfaces

Molecular-dynamics simulations (MDSs) and ab initiocalculations are used to investigate the adsorption behavior of C₆₀ molecules on a clean dimer-reconstructed (100)(2×1) diamond surface. C₆₀ molecules have some probability to be adsorbed on the diamond surface at low incident energy (6∼45 eV). Electron-density contours show strong chemical interaction between C₆₀ molecules and the substrate surface. The adsorption property depends strongly on the incident energy and the impacting point. An incident energy of 18 eV may be an appropriate energy to grow a sub-monolayer or monolayer C₆₀ film on a clean C(100)(2×1) surface at room temperature. Received: 5 July 2000 / Accepted: 17 October 2000 / Published online: 28 February 2001     

Intramolecular structures of C60 and C84 molecules on Si(1 1 1)-7 × 7 surfaces by scanning tunneling microscopy

The intramolecular features of carbon 60 and carbon 84 molecules on Si(1 1 1)-7 × 7 surfaces were studied under a UHV-scanning tunneling microscope. Carbon molecules preferentially appear in faulted halves, rather than in unfaulted halves and corner holes; they are embedded in silicon substrates. The orientation and details of the structure of carbon molecules are determined by applying various sample biases to the silicon substrate. As compared with other fullerenes, a bright pentagonal ring with nebulous clusters which represents the cage structure is clearly observed on top of carbon 60 molecules. The bright stripes associated with partitioned curves which depict eight features of asymmetrical C₈₄ molecules are also investigated on Si(1 1 1)-7 × 7 surfaces. The orientations and possible configurations of C₆₀ and C₈₄ are considered in this work. The energy differences for various features of C₆₀ and C₈₄ molecules are estimated and discussed. The corresponding models with respect to each intramolecular feature are proposed and compared with recent theoretical calculation.     

Experimental access to doped fullerene polymers

60 compound could be obtained by slow cooling the high temperature fcc phase and by quenching with subsequent annealing. The various phases after quenching and during annealing were studied in detail. No evidence for a direct doping of undoped C₆₀ to the polymeric AC₆₀ phase was found. Due to the local character of the doping process the formation of A₃C₆₀ clusters is observed. The same results were obtained from doping experiments performed with undoped polymeric structures like phototransformed and pressure polymerized C₆₀. Received: 6 October 1996/Accepted: 13 December 1996     

Scanning tunneling microscopy of fluorinated fullerene molecules on silicon surfaces

Scanning tunneling microscopy (STM) under ultra-high vacuum conditions is used to study the initial stages of adsorption of C₆₀F₁₈ and C₆₀F₃₆ fluorofullerene molecules on Si(111)-7 x 7 and Si(100)-2 x 1 surfaces. Spatially resolved STM images of individual molecules and ab initio calculations show that the fluorofullerene molecules interact with an Si surface, with the F atoms oriented toward the surface. The large electric dipole moment of the molecules induces strong polarization on the surface, but the charge transfer is weak. The presence of C₆₀F₃₆ isomers with different symmetry—T, C ₃, and C ₁—is revealed in STM images for the first time.