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.     

织构C60薄膜的生长与光致发光特性

用Hot Wal方法，在氟金云母单晶上生长出了（111）织构的C₆₀薄膜．用X射线衍射、Raman散射、扫描电子显微镜和原子力显微镜研究了织构C₆₀薄膜的结晶质量和结构特性．测量了织构C₆₀薄膜在室温300K和低温77K的光致发光光谱．对所得结果进行了分析与讨论 关键词：     

Frictional and atomic-scale study of C60 thin films by scanning force microscopy

Scanning force microscopy (SFM) was employed to characterize C₆₀ island films in an ultra-high vacuum (UHV). The initial growth stage of C₆₀ on NaCl cleavage faces and nanotribological properties of this solid lubricant are investigated. In comparison to the NaCl(001) face, higher friction is measured on the C₆₀ islands, resulting in a ratio of friction of 13 for NaClC₆₀. The friction coefficient of the (111) oriented C₆₀ island is determined to be 0.15±0.05. High-resolution SFM images reveal the hexagonal lattice of the unreconstructed (111) top surfaces and the overgrowth relationships of the C₆₀ islands.     

Temperature dependence of elastic moduli for solid C60

The attenuation and velocity of ultrasonic waves (at a frequency of ～4 MHz) along the 〈111〉 and 〈100〉 directions in solid C₆₀ single-crystal samples are measured in the temperature range 100–300 K. The temperature dependences of the complete set of elastic constants for C₆₀ fullerite are determined from the experimental data. It is shown that the specific features in the behavior of the elastic moduli near the orientational phase transition temperature are associated with different contributions of the relaxation processes to the effective elastic moduli. The activation volume and deformation potentials for the ground and excited states of the C₆₀ low-temperature phase are evaluated from the results obtained in this work and the data available in the literature.     

Cleavage of C<Subscript>60</Subscript> fullerite crystals

It is found that, under certain conditions, C₆₀ fullerite crystals can be cleaved along cleavage planes that are close-packed planes of the {111} type. Rigid gas-phase grown crystals exhibit good cleavage properties. In experiments with active compressive deformation, these crystals showed a high yield point τ_y = 2.65 MPa, a “parabolic” stress-strain curve, and brittle fracture after attaining a shear strain of about 8%. The fracture surface was clearly seen to have fragments parallel to the (111) plane. Typical microstructures observed in the cleavage plane are discussed: crystallographic cleavage steps, an indentation pattern, and a dislocation prick rosette. The fact that the activation volume V ? 60b³ is small (b is the Burgers vector of a dislocation) and strain-independent indicates the Peierls character of fullerite deformation or dislocation drag in a dense network of local defects.     

The compressive mechanical properties of Cn (n=20, 60, 80, 180) and endohedral M@C60 (M=Na,Al, Fe) fullerene molecules

The compressive mechanical properties of C_n (n = 20, 60, 80, 180) and endohedral M@C₆₀ (M = Na, Al, Fe) fullerene molecules are investigated using a quantum molecular dynamics (QMD) technique. Energy–strain curves, force–strain curves, endurance load, failure strain corresponding to the endurance load, and compressive stiffness of the fullerene molecules are obtained. The compressive mechanical properties of C₂₀, C₆₀, C₈₀, C₁₈₀ and M@C₆₀ (M = Na, Al, Fe) are discussed. The results show that the larger the magic number n of an empty fullerene, the higher its endurance load and compressive stiffness, but the lower its failure strain, and comparing to the empty C₆₀ fullerene, all the M@C60 molecules have greater endurance capability and failure strain.     

SiC film growth on Si(111) by supersonic beams of C 60

The development of electronic devices based on Silicon Carbide (SiC) has been strongly limited by the difficulties in growing high quality crystalline bulk materials and films. We have recently elaborated a new technique for the synthesis of SiC on clean Si substrates by means of supersonic beams of C₆₀: the electronic and structural properties of the film can be controlled by monitoring the beam parameters, i.e. flux and particles energy and aggregation state. SiC films were grown in Ultra High Vacuum on Si(111)-7×7, at substrates temperatures of 800 ^° C, using two different supersonic beams of C₆₀: He and H₂ have been used as seeding gases, leading to particles energy of 5 eV and 20 eV, respectively. Surface characterisation was done in situ by Auger and X-Ray photoelectron spectroscopy, as well as by low energy electron diffraction and ex situ by atomic force microscopy technique. SiC films exhibited good structural and electronic properties, with presence of defects different from the typical triangular voids. Received 20 November 2001     

Photophysics of C<Subscript>60</Subscript> and C<Subscript><Emphasis Type="Bold">60</Emphasis></Subscript><Superscript><Emphasis Type="Bold">-</Emphasis></Superscript> in faujasite zeolites

While the intercalation of C₆₀ and the formation of C ₆₀ ^- in the supercages of NaX and NaY are confirmed by using ¹²⁹Xe NMR and ESR, the photophysical properties of C₆₀ and C ₆₀ ^- are characterized by monitoring transient reflectance spectra and kinetics, fluorescence kinetics, and diffuse reflectance spectra. C ₆₀ ^- is considerably more abundant in NaY than in NaX. This difference is explained in terms of polarity difference between two zeolites. Both C₆₀ and C ₆₀ ^- have remarkably elongated excited-state lifetimes due to their collision-free environment in zeolitic nanocavities although C ₆₀ ^- has much shorter lifetimes than C₆₀. C ₆₀ ^- , in particular, shows intense absorption and emission due to its reduced symmetry in zeolites. Received 13 July 2001 and Received in final form 8 October 2001     

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     

Formation of highly crystalline C<Subscript>60</Subscript> molecular films on a Bi(0001)/Si(111) surface

The results of scanning tunneling microscopy (STM) investigation of controllable growth of C₆₀ adsorption on a Bi(0001)/Si(111) surface are reported. With the use of UHV STM, it has been shown that the most favorable sites for the initial stage of C₆₀ adsorption are the double steps and domain boundaries. At ∼1 monolayer C₆₀ coverage, the modulation pattern caused by the epitaxial relation between C₆₀ and Bi unit cells has been observed. An increase in the C₆₀ coverage up to several monolayers results in the formation of a highly crystalline molecular film. The text was submitted by the authors in English.     

Ferromagnetic properties of cyclically deformed Fe3Ge and Ni3Ge

The magnetisation behaviour of cyclically deformed and non-deformed Fe₃Ge and Ni₃Ge is examined at sufficiently low temperatures below the Curie point. Despite these two intermetallics having the same L1₂ structure, they are found to show quite different behaviour in their ferromagnetic properties; the spontaneous magnetisation (M _S) remains unaffected in the former whereas it decreases notably in the latter after cyclic deformation. The origin of the difference is investigated and attributed to the difference in operative shear planes. These are mainly on {001} planes without the introduction of notable amounts of anti-phase boundary (APB) tubes in Fe₃Ge and mainly on {111} planes with the introduction of a high density of APB tubes composed of {111} APBs in Ni₃Ge. The effects of cyclic deformation on the high-field susceptibility?χ?and the coercive force (H _C) are also discussed by taking into account the dislocation distributions introduced by the {001} and {111} slips.     

Adsorption and thermal decomposition of C60 on Co/Si(111)-7 × 7

We present a study on the adsorption and thermal decomposition of C₆₀ on Co covered Si(111)-7 × 7 using scanning tunneling microscopy and X-ray photoelectron spectroscopy. Co-induced magic clusters grown on Si(111)-7 × 7 are identified as a possible adsorption site where 51 ± 3% of C₆₀ molecules adsorb at room temperature. On Co/Si(111)-7 × 7, C₆₀ molecules start to decompose at 450 °C, and are completely dissociated to form SiC by 720 °C. This temperature is significantly lower than 910 °C at which C₆₀ completely dissociates on clean Si(111)-7 × 7. This is a possible low temperature method for growing crystalline SiC films using C₆₀ as a precursor molecule.     

Scanning tunneling microscopy/spectroscopy study of adsorption of C<Subscript>60</Subscript>F<Subscript>36</Subscript> molecules on the 7 × 7-Si(111) surface

Spatially resolved images of an individual C₆₀F₃₆ fluorofullerene molecules on Si(111)-7 × 7 surface have been obtained by means of scanning tunneling microscopy/spectroscopy (STM/STS). The presence of isomers with different symmetry (T, C ₃, C ₁) has been revealed in STM investigation of initial adsorption stage of C₆₀F₃₆ on silicon surface Si(111)-(7 × 7). The adsorbed fluorofullerene molecule can occupy any adsorption site of silicon surface (corner site, faulted half, unfaulted half) that indicates for strong molecule-substrate interaction. The HOMO-LUMO gap of the adsorbed C₆₀F₃₆ molecules have been estimated from current image tunneling spectroscopy (CITS) and z(V) with engaged feedback measurements. The value of HOMO-LUMO gap observed experimentally was 3 eV. The C₆₀F₃₆ molecules adsorption on Si(111)-(7 × 7) surface was stable and kept equilibrium configuration during several hours.     

Dipoles and band alignment for benzene/Au(111) and C<Subscript>60</Subscript>/Au(111) interfaces

A local orbital DFT-approach combined with a “scissor”-operator is used to obtain the Charge Neutrality Level and the screening parameter in the benzene/Au(111) and C₆₀/Au(111) interfaces. The “pillow” dipole and interface Fermi level are also calculated. The total dipole induced across the interface is compared with the experimental evidences: while the agreement for C₆₀/Au(111) is excellent, for benzene/Au(111), some discrepancies appear that are discussed in the light of other models.     

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.     

Structure and electrical characteristics of ICBD C60 films

Polycrystalline C₆₀ films are deposited onto a variety of substrates by ionized cluster beam deposition (ICBD) technique. The structure of the ICBD C₆₀ films are studied by transmission electron microscopy (TEM). The electrical characteristics of the ICBD C₆₀ films on silicon substrates are investigated by current-voltage (I–V) measurements. TheICBD C₆₀/p-Si and C₆₀/n-Si heterostructures show strong current rectification, which is analyzed using band theory.     

GaAs(100)衬底上C60单晶膜的取向生长

利用双温区真空蒸发沉积技术成功地在GaAs（100）衬底上实现了完全（111）取向的C₆₀单晶膜的生长．用扫描电子显微镜和Ｘ射线衍射技术对C₆₀单晶膜的形貌和结构进行了分析．结果表明：能实现C₆₀取向生长的衬底温度范围很窄，温度过高或过低都易造成晶粒的取向无序．对实验结果做出了合理的解释，并讨论了C₆₀单晶膜的生长机制 关键词：     

Structural features of the polymer-like phase of AC60 fullerides

A new approach is proposed for describing the deformation of the C₆₀ molecule in the polymer-like phase of the fullerides AC₆₀ (A=K, Rb). A discrete basis of orientational states of the molecule is introduced, and orientational ordering is described on the basis of a phenomenological theory. A symmetry analysis of the molecular vibrations in the Fm3m phase is performed. It is shown that small rotations of the C₆₀ can occur at a phase transition. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 2, 110–115 (25 July 1996)     

Room temperature supramolecular repositioning at molecular interfaces using a scanning tunneling microscope

Individual C₆₀ molecules adsorbed on a monolayer of 4,4′-dimethyl bianthrone first grown on Cu(111) have been repositioned at room temperature with the tip of a scanning tunneling microscope. The procedure can be applied to C₆₀ without disrupting the 4,4′-dimethyl bianthrone film. Controlled supramolecular repositioning at a molecular interface has allowed us to assemble lateral C₆₀ patterns that define a bimolecular C₆₀-4,4′-dimethyl bianthrone heterojunction on Cu(111).     

Mechanism of the formation of a diamond nanocomposite during transformations of C60 fullerite at high pressure

The results of an investigation of the transformation of C₆₀ fullerite to diamond under pressure through intermediate three-dimensionally polymerized and amorphous phases are reported. It is found that treatment of fullerite C₆₀ at pressures 12–14 GPa and temperatures ∼1400°C produces a nanocrystalline graphite-diamond composite with a concentration of the diamond component exceeding 50%. At lower temperatures (700–1200°C) nanocomposites consisting of diamondlike (sp ³) and graphitic (sp ²) amorphous phases are formed. The nanocomposites obtained have extremely high mechanical characteristics: hardness comparable to that of best diamond single crystals and fracture resistance two times greater than that of diamond. Mechanisms leading to the transformation of C₆₀ fullerite into diamond-based nanocomposites and the reasons for the high mechanical characteristics of these nanocomposites are discussed. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 11, 822–827 (10 June 1999)