The Rectification Studies on the P -Ion Implanted C60/Si Films

N-type doping of the C₆₀ films deposited on Si substrates has been achieved by 80 keV P⁺-ion implantation with doses of 2×10¹⁴ cm^-2 at room temperature. The heterostructures composed of the n-type doped C₆₀ films and n- or p-type Si(111), Si(100) substrates are studied in view of semiconductor heterojunctions. The rectification and other electrical characteristics of the P⁺-ion implanted n-C₆₀/n-(p-)Si heterostructures are disclosed by the current-voltage (I-V) measurements at room temperature. The n-C₆₀/p-Si heterostructures show stronger rectification than n-C₆₀/n-Si heterostructures and Si(111) substrates are found to be more suitable for forming n-C₆₀/Si heterostructures than Si(100) substrates.     

Imaging Fullerene C60 with Atomic Resolution Using a Scanning Tunnelling Microscope

C₆₀ was purified and imaged utilizing scanning tunnelling microscopy (STM) in a constant current mode. By fixing the Fullerenes on the substrate (“frozen state” - no movement or rotation), direct imaging of C₆₀ with atomic resolution was possible, showing one pentagon and one hexagon carbon ring of C₆₀.     

Growth of C60 single crystal films on metal substrates

High-quality C₆₀(111) single crystal films have been grown on Ni₃Fe(111), Ni₃Co(111) and Ni₃Fe(110) surfaces using hot-wall diffusion method. X-ray diffraction results show that well-ordered films can be obtained near 150°C on these substrates. The high quality of the films could be attributed to the perfect lattice match between C₆₀ film and substrates, low growth rate of C₆₀, and the suitable substrate temperature.     

Preparation and characterization of C60S16 and C70S48 thin films

In this study, we have investigated different methods for preparation of thin films of C₆₀ and C₇₀-sulfur compounds. Films of good quality were obtained by reaction of amorphous C₆₀ and C₇₀ films with a saturated sulfur solution in toluene at 40°C or with saturated sulfur vapour at a temperature of 140°C for several hours. The quality of the fullerene-sulfur films were strongly dependent on the microstructure of the initially deposited fullerene film and the synthesis temperature. X-ray diffraction analyses showed that both methods lead to the formation of films consisting of C₆₀S₁₆ and C₇₀S₄₈ (space groups C 2/c and Amm2, respectively). C₆₀S₁₆ films synthesised on Al₂O₃(012) and Si(100) substrates were texture-free while C₇₀S₄₈ films typically exhibited a preferential (100) orientation. The films were also characterised by Raman and IR- spectroscopy, which confirmed that the interactions between the fullerene molecules and the S₈ rings are weak. The fullerene-sulfur compounds were found to be unstable at high vacuum conditions. Both materials C₆₀S₁₆ and C₇₀S₄₈ are non-conductive at room temperature with conductivities less then 10⁻⁵ (Ω/cm).     

Stacking Defects in C60 Films

The structure of pollycrystalline C₆₀ films prepared by sublimation from 99.9% pure C₆₀ powder and from graphite soot was investigated by X-ray diffraction. A complex fcc (111) line was found in the former samples. Comparison of experimental and simulated (111) profiles allowed to assess quantitatively the degree of stacking disorder introduced during the growth of the film. Probabilities could be derived for continuation of already started fcc and hep sequences, thereby characterizing the statistical microstructure of the C₆₀ films. Also, the relative magnitudes of inter- and intra-layer disorder can be estimated. The films deposited from graphite soot show a high structural disorder.     

A three-step process for epitaxial growth of (111)-oriented C60 films on alkali–halide substrates

Epitaxial (111)-oriented C₆₀ films have been grown on alkali–halide substrates, KCl (100), KBr (100) and NaCl (100) by a three-step process: (1), substrate surface cleaning by high temperature heating; (2), initial deposition with a low deposition rate to grow two or three monolayers (ML); and (3), deposition with a high deposition rate to grow a film with expected thickness. It was found that (111)-oriented epitaxial C₆₀ films could be grown at low temperatures in a wide temperature range, from 40 to 120°C. By this three-step process, we can also grow epitaxial C₆₀ films at deposition rates as high as 35 Å/min.     

Synthesis of fullerenes from carbon powder by using high power induction thermal plasma

Radio frequency (rf) inductively coupled thermal plasma (ICTP) was used to fabricate fullerenes (C₆₀,C₇₀, etc.) by direct evaporation of carbon powder injected into the plasma. Spectroscopic observation of the plasma was made for molecular band spectra of C₂ and atomic lines of C. The formation of fullerenes C₆₀ and C₇₀ as well as higher fullerenes were checked and recognized by high performance liquid chromatography (HPLC) and time-of-flight mass spectrometer (TFMS). The suitable conditions for the synthesis of fullerenes within the experimental conditions adopted were 10-kPa plasma pressure, with a considerably higher flow rate of approximately 150 l/min for mixed-gas condition of Ar, He and CO₂, with carbon powder of average diameter 20 μm. The results showed that the productivity of fullerenes has a relation to the intensity of C₂ molecular and C atomic spectra from the induction plasma. Mixing of Si with C particles has a kind of role in enhancing the synthesis rate of fullerenes C₆₀, as well as the higher order fullerenes.     

Arc Synthesis of Silicon-Doped Heterofullerenes in Plasma at Atmospheric Pressure

For the first time, an arc synthesis at atmospheric pressure was carried out for obtaining silicon-doped heterofullerenes C₅₂Si₈ and C₆₂Si₈. These molecules were detected in a pyridine extract from soot by mass spectrometry in amounts of no more than 1%. The abundance ratio of the heterofullerenes is the same as that for C₆₀/C₇₀ mixture. An explanation of the absence of heterofullerenes with lower number of Si atoms is given.     

A Photovoltaic C60-Si Heterojunction

A heterojunction was prepared by depositing a thin film of C₆₀ on a p-Si substrate. Photovoltaic properties were observed using a UV-filtered solar simulator and natural sun light. Surface Photovoltage Spectroscopy was employed to distinguish between the nature of photoconversion in the C₆₀ and Si layers.     

GROUP TRANSFER AND DIMERIZATION PROCESSES OF C60(CN)2 UNDER ATMOSPHERIC PRESSURE IONIZATION CONDITIONS

Neutral and anionic C₆₀(CN)₂ were investigated with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) mass spectrometry. It was observed that its anions underwent cyano- group and oxygen transfer, and dimerization processes in ESI conditions to form C₆₀(CN)₃H^-, C₆₀(CN)₂(OH₂)^-, [C₆₀(CN)₃H]^-₂, [C₆₀(CN)₂(OH₂)]^-₂ and [(C₆₀)₂(CN)₂(OH)]^-. Meanwhile, neutral C₆₀(CN)₂, for which no signal was observed in ESIMS, showed a base peak corresponding to C₆₀(CN)₂Cl^- in APCIMS spectra with CHCl₃ used as solvent, while only a molecular ion peak corresponding to C₆₀(CN)^-₂ was observed for the toluene solution of neutral C₆₀(CN)₂ in the same conditions. Possible mechanisms for group transfer and dimerization were proposed based on these observations.     

Bromination of [60]Fullerene. I. High-Yield Synthesis of C60Brx (x=6, 8, 24)

The systematic study of the bromination of C₆₀ was performed under various experimental conditions. Application of some chloroarenes as reaction media resulted in the high-yield (70-96%) selective synthesis of C₆₀Br₆ and C₆₀Br₈. Direct bromination of fullerene yielded either C₆₀Br₈, C₆₀Br₁₄, or C₆₀Br₂₄ depending on the reaction time. Possible pathways of bromination of C₆₀Br₈ were analyzed using semiempirical (AM1) calculations, two most probable molecular structures are conjectured for the first isolated C₆₀Br₁₄.     

聚乙烯亚胺修饰富勒烯的制备及其对聚丙烯热氧稳定性的影响

利用聚乙烯亚胺(PEI)分子中活泼的?NH?与富勒烯(C₆₀)结构中C=C键之间的加成反应,制备了PEI修饰C₆₀杂化物(C₆₀?PEI),并采用FTIR、TEM等测试方法对C₆₀?PEI的分子结构和形态进行表征。采用熔融共混法制备了C₆₀?PEI/聚丙烯(PP)复合材料,并对其热性能和阻燃性能进行研究。热失重分析结果表明,C₆₀?PEI可以更有效地发挥C₆₀的自由基捕捉作用,对PP热稳定性的提高效果较C₆₀更明显;氧化诱导测试(OIT)结果表明,C₆₀?PEI/PP复合材料比C₆₀/PP复合材料具有更优异的抗氧性能;微型量热测试也表明,燃烧过程中C₆₀?PEI/PP复合材料比C₆₀/PP复合材料具有更低的热释放量。      

Electronic structure and electrical transport characteristics of C60, 2C60 and 4C60 fullerene molecules

The extended H?ckel method and the Green s function method were used to calculate the electronic structure and electrical transport of Au electrode-C₆₀, 2C₆₀ or 4C₆₀ fullerene-Au electrode systems. Furthermore, their electronic structure and electrical transport characteristics were compared and analyzed. The results show that (i) owing to the contact with the Au electrodes, the C₆₀, 2C₆₀ and 4C₆₀ molecules change in their electronic structures significantly, and their energy gaps between LUMO and HOMO are narrow; (ii) the bonding between C₆₀, 2C₆₀ or 4C₆₀ fullerene and Au electrodes is partially covalent and partially electrovalent; and (iii) the conductance of the three fullerenes conforms to the order of C₆₀>2C₆₀>4C₆₀.     

ISOLATION AND CHARACTERISATION OF C60(CF3)2

From the products of reactions of [60]fullerene with either K₂PtF₆ at 470 °C or AgF at 520 °C, we have isolated C₆₀(CF₃)₂, the simplest trifluoromethylfullerene, which gives a single ¹⁹F NMR line at -69.5 ppm. The HPLC retention time is less than that of C₆₀F₂ confirming the trend observed for other fluoro- vs. trifluoromethylfullerenes namely that the latter elute more rapidly. Other trifluoromethyl- containing species, C₆₀(CF₃)₄O, C₆₀F₅CF₃, C₆₀(CF₃)₄H₂, C₆₀(CF₃)₆H₂, and C₆₀(CF₃H)₃ were detected in the product mixture.     

Synthesis and Spectral Characterization of Difunctional Fullerenes

The oxidation of C₆₀ with m-chloroperbenzoic acid gave C₆₀O₂ with a high positional selectivity, as the ¹³C NMR analysis suggested. Diadducts C₆₀CCI₂O, C₆₀CCl₂(anthracene), C₆₀CCl₂[(CH₂CH₂)₂N₂], and C₆₀CCI₂[Pt-(PPh₃)₂] were synthesized, isolated, and characterized by negative ion FAB mass spectroscopy.     

Charge Transfer in Fullerene-Conducting Polymer Compositex: Electronic and Excitonic Properties

C₆₀ doping into conducting polymer with highly extended π-electron system in the main chain induces remarkable quenching of photoluminescence in conducting polymer and drastic enhancement of photoconductivity. These results can be explained in terms of photo-induced charge transfer between conducting polymer and C₆₀. That is, photoexcited excitons or exciton-polarons on conducting polymer are effectively dissociated at C₆₀ molecules transferring electrons to C₆₀. Photoexcitation of C₆₀ results in the transfer of hole from C₆₀ to conducting polymer. These novel C₆₀ doping effects have been observed not only in conducting polymers with non-degenerated ground state structures but also those with degenerated ground state structure such as di-substituted acetylene polymers with solitonic electronic systems.

Highly effective photo-induced charge transfer has been also observed in conducting polymer/C₆₀ heterojunctions, which are interpreted as donor (D)-acceptor (A) photocell. Based on this finding we have demonstrated an organic photovoltaic cell with D-A double heterojunction, Al/C₆₀/OEP/conducting polymer/TTO, in which OEP is octaethylporphine as an light absorbing antenna molecule. Novel characteristics have also been observed in various other junction devices utilizing C₆₀ doped conducting polymer.

Granular and multiphase superconductivity has been found in C₆₀-conducting polymer-alkali metal composites.

Effect of other type of fullerenes such as C₇₀, modified C₆₀ and C₆₀ polymers, and also effect of C₆₀ doping in polysilanes and their derivatives have also been studied.     

Raman Spectroscopy of the Charge Transfer Complex (TTF)x C60 Br8

We report Raman studies on powder samples of the charge transfer complex (TTF)_x C₆₀Br₈ at room temperature. The phonons show considerable softening with respect to the frequencies observed in the Raman spectrum of solid C₆₀ Brg. The strongest mode at 1464 cm^-1 in C₆₀Br₈ is red shifted to a doublet with peaks at 1414 and 1421 cm^-1, implying an average phonon softening Δω of -47 cm^-1. A comparison with the phonon softening of the corresponding A_g(2) mode in alkali-doped C₆₀ (Δω ~ - 36 cm^-1 for A₆C₆₀, A = K, Rb or Cs) suggests that 8 electrons are transferred per C₆₀Br₈ molecule in the charge transfer complex. The mode at 503 cm_--1 in C₆₀Br₈ is shifted upwards, similar to that in A₆ C₆₀ compounds.     

Arylation of [60]Fullerene with Br2/FeCl3/PhH: Formation of C58 Derivatives via CO Loss

Heating a mixture of [60]fullerene, bromine, ferric chloride and benzene under reflux for 24 h products a range of phenylated [60]fullerene derivatives. The main product is C₆₀Ph₅H but other components identified by mass spectrometry (and in some cases separated by HPLC) are: C_6oPh_n(n = 4, 6, 8, 10, 12), C₆₀Ph_nO₂(n = 4, 6, 8, 10, 12), C₆₀Ph_nOH (n = 7, 9, 11), C₆₀Ph_nH₂ (n = 4, 10), C₆₀Ph₄H₄, C₆₀Ph₅H₃, C₆₀Ph_n0₂H (n = 5, 9), C₆₀Ph₄C₆H₄O₂, C₆₀Ph₉OH₃, and C₆₀Ph₁₁ O₃H₂. In the corresponding reaction with toluene, the crude reaction mixture contained C₆₀(MeC₆H₄)₄ as a main product; C₆₀(ClC₆H₄)₅H was obtained from the reaction with chlorobenzene. Formation of these derivatives is believed to involve radical bromination of the fullerene, followed by electrophilic substitution of the hatogenofullerene into the aromatic, accompanied in some case by hydrolysis, elimination and epoxide formation; oxidation may also introduce ketone/dioxetane functionality. The EI mass spectra of C₆₀Ph₄O₂ and C₆₀Ph₈O₂show degradation to C₅₈Ph_n (n = 0-8), having structures believed to be related to the pseudofollerenes C₆₈Ph_n (n = 0-8) reported recently. These results suggest that some derivatisations of fullerenes confer stability, due to the relief of strain.     

Effects of C60, a Fullerene, on the Activities of Glutathione S-Transferase and Glutathione-Related Enzymes in Rodent and Human Livers

The effects of C₆₀, a fullerene, on the activities of glutathione 5-transferase (GST), glutathione peroxidase (GSH-Px) and glutathione reductase (GR) in rodent and human livers were investigated. the GST activity in rat liver towards frans-4-phenyl-3-buten-2-one and that in mouse liver towards ethacrynic acid were inhibited by C₆₀- the GST activity towards 1,2-dichloro-4-nitrobenzene, isomerase activity of GST towards androst-5-ene-3,17-dione, GSH-Px activity and GR activity were not affected by C₆₀ a kinetic study using purified mouse GST-π with ethacrynic acid (25-100 μM) as the substrate revealed that C₆₀ was a non-competitive inhibitor of the enzyme with a K_i = 48.8 ± 0.25 μM and a K_i = 47.9 ±0.18 μM. However, C₆₀ did not inhibit the activity of purified mouse GST-π towards l-chloro-2,4-dinitrobenzene. Thus, the inhibition by C₆₀ appears to be substrate-specific. In human liver, C₆₀ inhibited the GST activity towards ethacrynic acid, and moderately inhibited GSH-Px and GR activities.     

Thermally Activated Decay Processes of Isolated Superhot C60 in Molecular Beams

We have studied thermally activated decay processes of an ensemble of isolated superhot C₆₀ molecules in molecular beams by several different methods. Highly vibrationally excited C₆₀ molecules in effusive or supersonic beams (with average vibrational energy of 10-20 eV) were generated in an all ceramic, two-stage high temperature nozzle source. the decay kinetics due to various decay processes of the initially canonical ensemble was followed by a mass spectrometric methods for a large range of initial temperatures (T_o=1100 - 1950 K). the processes studied are: (1) fragmentation (C₂ emission) of the neutral C₆₀ (2) C₂ emission from the C⁺₆₀ ions (3) black-body like radiative cooling, and (4) delayed electron emission. the experiments described here are: (a) Depletion of the integrated C₆₀ flux. (b) Analysis of C₆₀ time-of-flight distributions. (c) Dependence of electron impact induced ionization/ fragmentation of C₆₀ upon its initial thermal excitation, and (d) Thermal energy dependence of delayed electron emission. It is shown that thermal kinetics models using a single set of independently measured parameters uniquely reproduce all the experimental observations. the models take into account the different cooling processes and their time evolution. We analyze in detail the evolution of the initially canonical vibrational energy distribution during the flight time to the detector as it is gradually being distorted due to evaporative and radiative cooling mechanisms. It is concluded that the correct parameters to be used for describing the thermally activated decay kinetics of superhot C₆₀ are activation energy of E_o = 4.3 - 4.8 eV for the neutral fragmentation channel C₆₀ → C₅₈ + C₂ and E₁=4.0 - 4.3 for the ion fragmentation channel C⁺₆₀→ C⁺₅₈ + C₂, and corresponding pre-exponential factors of A_o = A₁ = 2.5 × 10¹³ sec^-1. the emissivity coefficient for black body like radiation was found to be ε = 4.5 × 10^-5.