Gold cluster formation on C60 surfaces observed with scanning tunneling microscopy: Au-cluster beads and self-organized structures

The growth mechanism of Au-clusters on fullerene layers has been investigated by scanning tunneling microscopy in ultrahigh vacuum at room temperature. The fullerene layers, which serve as substrates, are formed on a graphite surface and exhibit the typical combination of round and fractal shapes, and small sections of the original graphite substrate are exposed. The immobile Au-clusters are concentrated on the C₆₀ terminated surface section, and the original fullerene island structures are preserved. A preferential nucleation of Au-clusters is observed at the C₆₀-graphite edges while the C₆₀-C₆₀ edges remains undecorated. These Au-clusters are placed directly on the edge and shared by the graphite and fullerene layer. They form bead-like structures, which densely populate this edge, while the first layer C₆₀ islands are clearly depleted of Au-clusters. A roughness analysis of the fullerene surface indicates the presence of Au atoms (or very small clusters), which are embedded in the fullerene surface, and likely situated in the troughs in between the large molecules. These Au atoms are highly mobile and cannot be individually resolved at room temperature. The analysis of the spatial and size distributions of Au-clusters provides the basis for the development of a qualitative model, which describes the relevant surface processes in the Au-fullerene system. The simultaneous deposition of Au and fullerene on graphite leads to the formation of highly organized structures, in which Au-clusters are embedded in a ring of fullerene molecules with a constant width of about 4 nm. The mechanism for the formation of these structures is highly speculative at present and further experiments will be pursued in the near future. A comprehensive analysis of the Au-C₆₀ system is presented, which contributes to the advancement in our understanding of the metal-fullerene interaction and furthers the development of composite materials of interest in the synthesis of solar cells and metal contacts to organic materials.     

Effect of oxygen on the electrophysical properties of some carbon allotropes (graphite and C60 fullerene)

The electrophysical properties of powder samples of graphite and C₆₀ fullerene have been studied in vacuum, oxygen ambient, and air. Room-temperature conduction of the samples has a percolative character. An increase of temperature brings about an increase of sample conductivity caused by oxygen desorption from the bulk. A peak-shaped feature not observed before has been found in the temperature behavior of the resistance of finely dispersed C₆₀ and graphite powder samples in the T=310–340 K interval. Oxygen atoms were found to be involved in charge transport in powder samples of graphite and C₆₀ fullerene through their electrical activity on the surface of grains differing in size. Fiz. Tverd. Tela (St. Petersburg) 39, 1703–1705 (September 1997)     

Electrical and mechanical properties of C70 fullerene and graphite under high pressures studied using designer diamond anvils

We compare electrical and mechanical properties of C70 fullerene with high purity graphite to 48 GPa at room temperature using designer diamond anvils with embedded electrical microprobes. The electrical resistance of C70 shows a minimum at 20 GPa with transformation to an amorphous insulating phase complete above 35 GPa, while graphite remains conducting. Nanoindentation shows hardness values 220 times larger for the pressure quenched amorphous phase than for similarly treated graphite. Our studies establish that the amorphous carbon phase produced from C70 has unique properties not attainable from graphite.     

Effect of C60 fullerene, fullerene-containing soot, and other carbon materials on the sliding edge friction of metals

A comparative study of different carbon materials (C₆₀ fullerene; soot, both with and without fullerenes; graphite; and industrial carbon black) as additives to industrial lubricating oils has been carried out for copper-steel and steel-steel sliding couples. The soot containing fullerene and the powder of pure fullerene produce a noticeable improvement in the antifriction and antiwear properties of steel-steel and steel-copper couples, especially under heavy loads and pressures at the contact. The greatest improvement was observed for the steel-steel couple. Structural-mechanical studies were carried out for copper riders and it has been demonstrated by several methods that the addition of the C₆₀ fullerene (pure fullerene or as a fullerene-containingsoot) creates a fullerene-polymer film on the frictional surface about 1000 Å thick, which has a protective effect.     

Effect of fullerenes on the activation energy of the graphite-diamond phase transition

The modification of graphite used in diamond synthesis with low concentrations of the fullerene C₆₀-C₇₀ extract (from 0.045 to 0.225 wt % of graphite mass) in the presence of a Ni-Mn metal catalyst at a pressure of 5 GPa in the temperature range 1600–1800 K is found to decrease the activation energy of the graphite-diamond phase transition from 160 ± 40 to 100 ± 40 kJ/mol.     

还原温度对氧化石墨烯结构及室温下H_2敏感性能的影响

以氧化石墨凝胶制备的氧化石墨烯(GO)溶胶为前驱体,在100—350℃温度下还原获得不同还原程度的还原氧化石墨烯(rGO)样品,并采用旋涂工艺制备还原氧化石墨烯气敏薄膜元件.采用X射线衍射、拉曼光谱、傅里叶变换红外光谱和气敏测试等手段研究还原温度对样品结构、官能团和气敏性能的影响.结果表明:经热还原处理的氧化石墨烯结构向较为有序的类石墨结构转变,还原温度为200℃时,样品处于GO向rGO转变的过渡阶段,还原温度达到250℃时,则表现出还原氧化石墨烯特性;无序程度随还原温度的升高先由0.85增大至1.59,随后减小至1.41,总体呈现增加趋势;氧化石墨烯表面含氧官能团随还原温度的升高逐渐热解失去,不同含氧官能团的失去温度范围不同;热还原氧化石墨烯具有优异的室温H_2敏感性能,随着还原温度的升高,元件灵敏度逐渐减小,响应-恢复时间逐渐增大,最佳灵敏度为88.56%,响应时间为30 s.     

Phase Transitions in a Mixture of Amorphous C<Subscript>60</Subscript> and C<Subscript>70</Subscript> Fullerene Phases at High Temperatures and Pressures

Phase transitions in two types of amorphous fullerene phases (C₆₀–C₇₀ (50/50) mixtures and an amorpous C₇₀ fullerene phase) are studied via neutron diffraction at pressures of 2–8 GPa and temperatures of 200–1100°C. Fullerenes are amorphized by grinding in a ball mill and sintered under quasi-hydrostatic pressure in a toroidal-type chamber. Diffraction studies are performed ex situ. It is shown that the amorphous phase of fullerenes retains its structure at temperatures of 200–500°C, and amorphous graphite is formed at 800–1100°C with a subsequent transition to crystalline graphite. This process is slow in a mixture of fullerenes, compared to C₇₀ fullerene. According to neutron diffraction data, the amorphous graphite formed from amorphous fullerene phases has anisotropy that is much weaker in a fullerene mixture.     

Electronic structure of graphite nanopipes

A recursion method is used for calculating the electron-state density n(E) of carbon in diamond, graphite, C₆₀ fullerene, and graphite nanopipes of various structures and diameters. The calculated n(E) for diamond, graphite, and fullerene are compared with experimental data. The distinctive features of the electron-state density n(E) in graphite nanopipes are discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 1118–1121 (June 1997)     

Synthesis of germanium encapsulated fullerene

A method has been described for encapsulating Ge in a fullerene cage using GeO₂ and a graphite composite rod as anode and graphite as cathode. Annealing in an inert atmosphere before arcing, and the amount of GeO₂ in the rod determined the yield of Ge doped metallofullerene. Solvent extraction using soxlet in inert atmosphere followed by calcination in air was used to isolate metallofullerene from the soot. The insertion of Ge inside the fullerene was proven by ultra violet–visible absorption spectroscopy, matrix assisted laser desorption ionization-time of flight mass spectroscopy, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy.     

Some comparative thermodynamic characteristics of fullerite and various covalent elements

Measurements of the specific heat and elastic wave velocities for a C₆₀ fullerene sample treated at high pressure and temperature are used to estimate the Debye temperature and the function ΔC=C _p−C _v, and also to calculate the thermal expansion work in the ideal approximation. Similar calculations were made for graphite, diamond, silicon, germanium, and various refractory metals. The results were used to draw qualitative conclusions on the structural stability of a new material obtained from fullerene C₆₀ which possesses extremely high hardness. Fiz. Tverd. Tela (St. Petersburg) 40, 1387–1389 (July 1998)     

On the energy stability of carbon nanoclusters

A method for evaluating the energy stability of carbon nanoclusters is proposed. The stabilities of the nanoclusters with different structures, such as diamond and graphite, tubulenes and graphite, are compared. Two series of stable clusters with new structures, namely, alm-ene and alm-ine, are derived. A comparison is performed for small graphite clusters containing boron atoms that play a significant role in the reaction of fullerene formation.     

Effect of deuterium on phase transformations in fullerenes at high temperatures and high pressures

The effect deuterium has on phase transformations is studied for amorphous and crystalline fullerenes C₆₀ and C₇₀ at high temperatures of up to 1300°C and high pressures (2–8 GPa). Amorphous fullerene phases are obtained via long grinding in a planetary mill. Structure is studied by means of neutron diffraction. In all cases, amorphous graphite (nanographite) forms in the temperature range of 800–1100°C. This material has different diffraction spectra distinguished by the heights of the halos observed on the graphite diffraction maxima and their relative intensities. These spectra (the structure of nanographite) are affected by preliminary amorphization, the number of carbon atoms in the fullerenes (C60 or C70), and the introduction of deuterium atoms. The different spectra of amorphous (disordered) graphite testify to its varying structure.     

Arc discharge sputtering of schungites

The schungite structure is shown to be modified in an arc discharge in an inert gas atmosphere. As a result of the direct effect of the arc discharge, some portion of the schungite material transforms locally into rhombohedral graphite. The spectral dependence of the optical transmission of the solutions of graphite soot and schungite soot in toluene is measured. X-ray diffraction patterns of the schungite soot and graphite soot contain a broad maximum at small scattering angles, which indicates the presence of fullerene molecules.     

高温高压条件下富勒碳的相变

 利用工业金刚石高压合成装置研究了C60和巴基管在高温（1 450 ℃）高压（5~6 GPa）下的相变。SEM、XRD和Uv/Vis分析结果表明，试样中有大量金刚石生成和少量石墨出现，同时有极少部分C60保留了下来；所生成的金刚石晶体同时以二维台阶和螺旋台阶方式生长。     

Graphitization of a diamond surface upon high-dose ion bombardment

Results from structural and morphological studies, measurements of the sheet electrical resistance, and estimating resistivity ρ_m of a graphite-like conducting surface layer formed upon high-dose irradiation of the (111) face of a synthetic diamond with Ar⁺ ions at an energy of 30 keV and a target temperature of 400°C are presented. It is found that the orienting effect of the diamond lattice is visible in the suppression of the formation of graphite crystallites with axis c perpendicular to the surface. The thickness of the modified layer is 40–50 nm, and its sheet resistance is 0.5 kΩ/sq. Resistivity ρ_m = 20–25 μΩ m of the modified layer lies within the range of ρ values of graphite and glassy carbon materials.     

In situ electrical resistance and activation energy of solid C_(60) under high pressure

The in situ electrical resistance and transport activation energies of solid C60 fullerene have been measured under high pressure up to 25 GPa in the temperature range of 300-423 K by using a designed diamond anvil cell. In the experiment, four parts of boron-doped diamond films fabricated on one anvil were used as electrical measurement probes and a W-Ta thin film thermocouple which was integrated on the other diamond anvil was used to measure the temperature. The current results indicate that the measured high-pressure resistances are bigger than those reported before at the same pressure and there is no pressure-independent resistance increase before 8 GPa. From the temperature dependence of the resistivity, the C60 behaviors as a semiconductor and the activation energies of the cubic C60 fullerene are 0.49, 0.43, and 0.36 eV at 13, 15, and 19 GPa, respectively.     

Controllable synthesis of fullerene nano/microcrystals and their structural transformation induced by high pressure

Fullerene molecules are interesting materials because of their unique structures and properties in mechanical, electrical, magnetic, and optical aspects. Current research is focusing on the construction of well-defined fullerene nano/microcrystals that possess desirable structures and morphologies. Further tuning the intermolecular interaction of the fullerene nano/microcrystals by use of pressure is an efficient way to modify their structures and properties, such as creation of nanoscale polymer structures and new hybrid materials, which expands the potential of such nanoscale materials for di- rect device components. In this paper, we review our recent progress in the construction of fullerene nanostructures and their structural transformation induced by high pressure. Fullerene nano/microcrystals with controllable size, morphology and structure have been synthesized through the self-assembly of fullerene molecules by a solvent-assisted method. By virtue of high pressure, the structures, components, and intermolecular interactions of the assemblied fullerene nano/microcrystals can be finely tuned, thereby modifying the optical and electronic properties of the nanostructures. Several examples on high pressure induced novel structural phase transition in typical fullerene nanocrystals with C60 or C70 cage serving as build- ing blocks are presented, including high pressure induced amorphization of the nanocrystals and their bulk moduli, high pressure and high temperature （HPHT） induced polymerization in C60 nanocrystals, pressure tuned reversible polymeriza- tion in ferrocene-doped C60/C70 single crystal, as well as unique long-range ordered crystal with amorphous nanoclusters serving as building blocks in solvated C60 crystals, which brings new physical insight into the understanding of order and disorder concept and new approaches to the design of superhard carbon materials. The nanosize and morphology effects on the transformations of fullerene nanocrystals have also been discussed. These results provide the foundation for the fabrication of pre-designed and controllable geometries, which is critical in fullerenes and relevant materials for designing nanometer-scale electronic, optical, and other devices.     

Effect of Amphiphilic Polymer Modified Graphene Surfactant on the Thermal,Viscoelastic and Tensile Properties of Nitrile Latex Nanocomposites

Carboxylated butadiene-nitrile latex (CBNL) elastomers possess several unique characteristics including excellent abrasion resistance and oil resistance. They are used in a wide variety of commercial and Defense applications. In this work, the effect of a newly developed graphene surfactant (GOS) on the thermal, mechanical and viscoelastic properties of vulcanized latex nanocomposites was studied. The latex was synthesized by emulsion polymerization and the vulcanized film without any filler had a tensile strength (TS) of 2.40?MPa and strain at break of 107%. Graphite filler (8?wt%) in combination with 2.6?wt% of GOS, added to the latex, increased the TS to 5.2?MPa and to 7.5?MPa with 10?wt% of the GOS, while the elongation at break was reduced to 48% and 30% for the latex nanocomposites, respectively. The vulcanized film without any graphite, but with 2.8?wt% of GOS had a TS of 7.8?MPa and a marginally increased elongation at break (88%), as compared to the graphite filled composites. The nanocomposites with graphite and GOS also showed higher damping characteristics, as indicated by the width of the tan δ peak, spanning over a broad temperature range of 100?°C for the sample with 2.6?wt% GOS and 8?wt% graphite. In summary, the work reports the development of potentially valuable damping materials from carboxylated nitrile latex using an amphiphilic polymer modified graphene surfactant in combination with graphite.     

基于拉曼热测量技术的铜基复合物法兰GaN基晶体管的热阻分析

采用拉曼热测量技术结合有限元热仿真模型,分析比较新型铜/石墨复合物法兰封装与传统铜钼法兰封装的GaN器件的结温与热阻,发现前者的整体热阻比铜钼法兰器件的整体热阻低18.7%,器件内部各层材料的温度分布显示铜/石墨复合物法兰在器件中的热阻占比相比铜钼法兰在器件中的热阻占比低13%,这证明使用高热导率铜/石墨复合物法兰封装提高GaN器件热扩散性能的有效性.通过对两种GaN器件热阻占比的测量与分析,发现除了封装法兰以外,热阻占比最高的是GaN外延与衬底材料之间的界面热阻,降低界面热阻是进一步提高器件热性能的关键.同时,详细阐述了使用拉曼光热技术测量GaN器件结温和热阻的原理和过程,展示了拉曼光热技术作为一种GaN器件热特性表征方法的有效性.     

New trends in high-order harmonics generation using the mid-infrared pulses propagating through the laser-produced plasmas

Various recently emerged applications of mid-infrared pulses for high-order harmonic generation in laser plasmas produced on the surfaces of various materials are reviewed. Among them are (a) the highorder harmonic generation in Ag, Sn, fullerene, and graphene nanoparticle-containing plasmas using tunable two-color mid-infrared pulses, (b) efficiency dependence on the generating particle properties in the case of two-color high-harmonic generation of the longer-wavelength radiation in the plasmas, and (c) high-order sum and difference frequency generation using tunable two- and three-color commensurate and incommensurate mid-infrared pumps of graphite plasma. These studies demonstrate the perspectives of the frequency conversion of mid-infrared radiation in the extended laser-produced plasmas.