Superconductivity at 45 k in rb/tl codoped c60 and c60/c70 mixtures

The appearance of superconductivity at relatively high temperatures in alkali metal-doped C(60) fullerene provides the challenge to both understand the nature and origin of the superconductivity and to determine the upper limit of the superconducting transition temperature (T(c)). Towards the latter goal, it is shown that doping with potassium-thallium and rubidium-thallium alloys in the 400 to 430 degrees C temperature range increases the T(c) of C(60)/C(70) mixtures to 25.6 K and above 45 K, respectively. Similar increases in T(c) were also observed upon analogous doping of pure C(60). Partial substitution of potassium with thallium in interstitial sites between C(60) molecules is suggested by larger observed unit cell parameters than for the K(3)C(60) and K(4)C(60) phases. Contrary to previous results for C(60) doped with different alkali metals, such expansion does not alone account for the changes in critical temperature.     

Photoemission Spectra and Electronic Properties of KxC60

Photoemission spectra of vacuum deposited layers of C(60), before and after exposure to K vapor, show that the K donates its conduction electron into the band derived from the lowest unoccupied molecular orbital. A compound with composition of K(3)C(60), corresponding to the maximum conductivity, has been prepared. In it the potassium atoms presumably occupy both the octahedral and the two tetrahedral interstitial sites of the face-centered-cubic (fcc) C(60) structure.     

New phases of c60 synthesized at high pressure

The fullerene C(60) can be converted into two different structures by high pressure and temperature. They are metastable and revert to pristine C(60) on reheating to 300 degrees C at ambient pressure. For synthesis temperatures between 300 degrees and 400 degrees C and pressures of 5 gigapascals, a nominal face-centered-cubic structure is produced with a lattice parameter a(o) = 13.6 angstroms. When treated at 500 degrees to 800 degrees C at the same pressure, C(60) transforms into a rhombohedral structure with hexagonal lattice parameters of a(o) = 9.22 angstroms and c(o) = 24.6 angstroms. The intermolecular distance is small enough that a chemical bond can form, in accord with the reduced solubility of the pressure-induced phases. Infrared, Raman, and nuclear magnetic resonance studies show a drastic reduction of icosahedral symmetry, as might occur if the C(60) molecules are linked.     

Electrical resistivity and stoichiometry of kkhgr c60 films

Electrical resistances of polycrystalline fullerene (C(60)) films were monitored while the films were being doped in ultrahigh vacuum with potassium from a molecular-beam effusion source. Temperature- and concentration-dependent resistivities of K(chi) C(60) films in equilibrium near room temperature were measured. The resistance changes smoothly from metallic at chi approximately 3 to activated as chi --> = 0 or chi --> 6. The minimum resistivity for K(3)C(60) films is 2.2 microohm-centimeters, near the Mott limit. The resistivities are interpreted in terms of a granular microstructure where K(3)C(60) regions form nonpercolating grains, except perhaps at chi approximately 3. Stoichiometries at the resistivity extrema were determined by ex situ Rutherford backscattering spectrometry to be chi = 3 +/- 0.05 at the resistance minimum and chi = 6 +/- 0.05 at the fully doped resistance maximum.     

Radical reactions of c60

Photochemically generated benzyl radicals react with C(60) producing radical and nonradical adducts Rn C(60) (R = C(6)H(5)CH(2)) with n = 1 to at least 15. The radical adducts with n = 3 and 5 are stable above 50 degrees C and have been identified by electron spin resonance (ESR) spectroscopy as the allylic R(3)C(60)(.) (3) and cyclopentadienyl R(5)C(60)(.) (5) radicals. The unpaired electrons are highly localized on the C(60) surface. The extraordinary stability of these radicals can be attributed to the steric protection of the surface radical sites by the surrounding benzyl substituents. Photochemically generated methyl radicals also add readily to C(60). Mass spectrometric analyses show the formation of (CH(3))nC(60) with n = 1 to at least 34.     

Synthesis and Single-Crystal X-ray Structure of a Highly Symmetrical C60 Derivative, C60Br24

C(60) and liquid bromine react to form C(60)Br(24), a crystalline compound isolated as a bromine solvate, C(60)Br(24)(Br(2))(x), The x-ray crystal structure defines a new pattern of addition to the carbon skeleton that imparts a rare high symmetry. The parent C(60) framework is recognizable in C(60)Br(24), but sp(3) carbons at sites of bromination distort the surface, affecting conformations of all of the hexagonal and pentagonal rings. Twenty-four bromine atoms envelop the carbon core, shielding the 18 remaining double bonds from addition. At 150 degrees to 200 degrees C there is effectively quantitative reversion of C(60)Br(24) to C(60) and Br(2).     

Packing C60 in boron nitride nanotubes

We have created insulated C60 nanowire by packing C60 molecules into the interior of insulating boron nitride nanotubes (BNNTs). For small-diameter BNNTs, the wire consists of a linear chain of C60 molecules.With increasing BNNT inner diameter, unusual C60 stacking configurations are obtained (including helical, hollow core, and incommensurate) that are unknown for bulk or thin-film forms of C60.C60 in BNNTs thus presents a model system for studying the properties of dimensionally constrained "silo" crystal structures. For the linear-chain case, we have fused the C60 molecules to form a single-walled carbon nanotube inside the insulating BNNT.     

Orientational and Magnetic Ordering of Buckyballs in TDAE-C60

Spin ordering in the low-temperature magnetic phase is directly linked to the orientational ordering of C(60) molecules in organically doped fullerene derivatives. Electron spin resonance and alternating current susceptometry measurements on tetrakis(dimethylamino)ethylene-C(60) (TDAE-C(60)) (Curie temperature T(c) = 16 kelvin) show a direct coupling between spin and merohedral degrees of freedom. This coupling was experimentally demonstrated by showing that ordering the spins in the magnetic phase imprints a merohedral order on the solid or, conversely, that merohedrally ordering the C(60) molecules influences the spin order at low temperature. The merohedral disorder gives rise to a distribution of pi-lectron exchange interactions between spins on neighboring C(60) molecules, suggesting a microscopic origin for the observed spinglass behavior of the magnetic state.     

Order-disorder transition in polycrystalline c60 films

High-resolution Raman spectroscopy of polycrystalline films of C(60) deposited under ultrahigh-vacuum conditions show that the spectrum below 244 +/- 3 kelvin consists of a superposition of two components whose relative contributions are temperature-dependent. The spectrum of the more intense of the two components is similar to that obtained for air- or oxygen-exposed samples of C(60) at room temperature, whereas the spectrum above 244 +/- 3 kelvin corresponds to one previously reported for oxygen-free samples of C(60). The results may indicate an order-disorder phase transition involving the percolation of a cluster of C(60) molecules engaged in coherent Raman scattering.     

Electrical Resistivity and Stoichiometry of CaxC60 and SrxC60 Films

The temperature- and concentration-dependent resistivities of annealed CaxC(60) and SrxC(60) films were measured near room temperature. Resistivity minima were observed at x = 2 and 5. The resistivities of these films were rho(min) approximately 1 ohm-centimeter for x = 2 and rho(min) approximately 10(-2) ohm-centimeter for x = 5. This latter value is comparable to the resistivities found in similar experiments on K(3)C(60) films. There is a maximum in the resistivity between x = 2 and 3, and another at x approximately 7. The conductivity is activated over the whole range of compositions, and the activation energy scales with the logarithm of the resistivity. The results suggest that the conductivity and superconductivity observed in Ca(5)C(60) are associated with the population of bands derived from the t(1g) level of C(6O).     

Formation of fullerides and fullerene-based heterostructures

Two potassium fulleride phases, metallic K(3)C(60) and nonmetallic K(6)C(60), are formed when potassium is incorporated into thin C(60) films under ultrahigh vacuum conditions. Phase separation is observed for intermediate stoichiometries. Results obtained for the C(60)-K(3)C(60) heterostructure demonstrate that it is stable against potassium migration from the K(3)C(60) phase. In contrast, the C(60)-K(6)C(60) interface is not stable and K(3)C(60) is formed.     

C60H2: Synthesis of the Simplest C60 Hydrocarbon Derivative

The reaction of C(60) with BH(3): tetrahydrofuran in toluene followed by hydrolysis yielded C(60)H(2). This product was separated by high-performance liquid chromatography and characterized as the addition product of H(2) to a 6,6-ring fusion (1alb isomer). The (1)H nuclear magnetic resonance (NMR) spectrum of the product remained a sharp singlet between -80 degrees and +100 degrees C, which suggests a static structure on the NMR time scale. Hydrolysis of the proposed borane addition product with acetic acid-d(1) or D(2)O yielded C(60)HD, and its (3)J(HD) coupling constant is consistent with vicinal addition. The observation of a single C(60)H(2) isomer is in complete agreement with earlier calculations that indicated that at most 2 of the 23 possible isomers of C(60) would be observable at equilibrium at room temperature. These results suggest that organoborane chemistry may be applied to further functionalization of fullerenes.     

Orientational Disorder of C60 in Li2CsC60

The x-ray diffraction of the nonsuperconducting ternary fulleride Li(2)CsC(60) reveals at room temperature a face-centered-cubic (Fm3m) disordered structure that persists to a temperature of 13 Kelvin. The crystal structure is best modeled as containing quasispherical [radius of 3.556(4) angstroms] C(60)(3-) ions, in sharp contrast to their orientational state in superconducting face-centered-cubic K(3)C(60) (merohedral disorder) and primitive cubic Na(2)CsC(60) (orientational order). The orientational disorder of the carbon atoms on the C(60)(3-) sphere was analyzed with symmetry-adapted spherical-harmonic functions. Excess atomic density is evident in the <111> directions, indicating strong bonding Li(+)-C interactions, not encountered before in any of the superconducting alkali fullerides. The intercalate-carbon interactions and the orientational state of the fullerenes have evidently affected the superconducting pair-binding mechanism in this material.     

Tunneling Spectroscopy of M3C60 Superconductors: The Energy Gap, Strong Coupling, and Superconductivity

Tunneling spectroscopy has been used to characterize the magnitude and temperature dependence of the superconducting energy gap (triangle up) for K(3)C(60) and Rb(3)C(60). At low temperature the reduced energy gap, 2triangle upkappaT(c) (where T(c) is the transition temperature) has a value of 5.3 +/- 0.2 and 5.2 +/- 0.3 for K(3)C(60) and Rb(3)C(60), respectively. The magnitude of the reduced gap for these materials is significantly larger than the value of 3.53 predicted by Bardeen-Cooper-Schrieffer theory. Hence, these results show that the pair-coupling interaction is strong in the M(3)C(60) superconductors. In addition, measurements of triangle up(T) for both K(3)C(60) and Rb(3)C(60) exhibit a similar mean-field temperature dependence. The characterization of triangle up and triangle up(T) for K(3)C(60) and Rb(3)C(60) provides essential constraints for theories evolving to describe superconductivity in the M(3)C(60) materials.     

Probing c60

Experiments involving the laser vaporization of graphite have indicated that one particular duster of carbon, C(60), is preeminently stable; this special stability may be evidence that C(60) can readily take the form of a hollow truncated icosahedron (a sort of molecular soccerball). If true, this structure for C(60) would be the first example of a spherical aromatic molecule. In fact, because of symmetry properties unique to the number 60, it may be the most perfecty spherical, edgeless molecule possible. Its rapid formation in condensing carbon vapors and its extreme chemical and photophysical stability may have far-reaching implications in a number of areas, particularly combustion science and astrophysics. For these reasons C(60) and other dusters of carbon have continued to be the subject of intense research. This article provides a short review of the many new experimental probes of the properties of C(60) and related carbon dusters.     

Charge Donation by Calcium into the t1g Band of C60

Photoemission spectra of compounds prepared by the reaction of C(60) films with calcium show two distinct metallic phases, whereas alkali-doped C(60) films have only one. In the first phase the bulk t(1u) band, derived from the lowest unoccupied molecular orbital of C(60), is partially occupied. This is followed by an insulating phase that has the composition Ca(3)C(60) in which the t(1u) band is filled and has properties analogous to those of K(6)C(60). Continued exposure to calcium produces a second metallic phase in which electrons are donated into the t(1g) band. The superconductivity of Ca(5)C(60) is associated with the t(1g) band.     

Spherical bilayer vesicles of fullerene-based surfactants in water: a laser light scattering study

The low solubility of fullerenes in aqueous solution limits their applications in biology. By appropriate substitution, the fullerenes can be transformed into stabilized anions that are water soluble and can form large aggregated structures. A laser light scattering study of the association behavior of the potassium salt of pentaphenyl fullerene (Ph5C60K) in water revealed that the hydrocarbon anions Ph5C60- associate into bilayers, forming stable spherical vesicles with an average hydrodynamic radius and a radius of gyration of about 17 nanometers at a very low critical aggregation concentration of less than 10(-7) moles per liter. The average aggregation number of associated particles in these large spherical vesicles is about 1.2 x 10(4).     

Existence of an orientational electric dipolar response in c60 single crystals

The dielectric constant in and conductivity sigma of undoped C(60) single crystals have been measured as a function of temperature, 10 K < T < 330 K, and frequency, 0.2 kilohertz < f < 100 kilohertz. On cooling below the first-order structural phase transition at 260 K, a Debye-like relaxational contribution to the dielectric response is observed, which requires the presence of permanent electric dipoles. The relaxation rate is thermally activated with a broad distribution of energies centered at 270 millielectron volts. The existence of a dipole moment in C(60) is unexpected, because it is precluded by symmetry for the pure ordered cubic phase. These data suggest that the high degree of frozen-in orientational disorder of the C(60) molecules is responsible for the existence of electric dipolar activity.     

13C NMR Spectroscopy of KxC60: Phase Separation, Molecular Dynamics, and Metallic Properties

The results of (13)C nuclear magnetic resonance (NMR) measurements on alkali fullerides KxC(60) are reported. The NMR spectra demonstrate that material with 0 < x < 3 is in fact a two-phase system at equilibrium, with x = 0 and x = 3. NMR lineshapes indicate that C(3-)(60) ions rotate rapidly in the K(3)C(60) phase at 300 K, while C(6)-(60) ions in the insulating K(6)C(60) phase are static on the time scale of the lineshape measurement. The temperature dependence of the (13)C spin-lattice relaxation rate in the normal state of K(3)C(60) is found to be characteristic of a metal, indicating the important role of the C(3-)(60) ions in the conductivity. From the relaxation measurements, an estimate of the density of electronic states at the Fermi level is derived.     

Atomic Force Microscope Studies of Fullerene Films: Highly Stable C60 fcc (311) Free Surfaces

Atomic force microscopy and x-ray diffractometry were used to study 1500 A-thick films of pure C(60) grown by sublimation in ultrahigh vacuum onto a CaF(2) (111) substrate. Topographs of the films did not reveal the expected close-packed structures, but they showed instead large regions that correspond to a face-centered cubic (311) surface and distortions of this surface. The open (311) structure may have a relatively low free energy because the low packing density contributes to a high entropy of the exposed surface.