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IT has been demonstrated1–6 that solid C60 can be readily intercalated with group IA alkali metals to give metallic or insulating compounds, depending on the dopant concentration. The metal atoms diffuse into tetrahedral and octahedral interstitial sites of the C60 lattice with little disturbance to the face-centred cubic (f.c.c.) packing7. The A3C60f.c.c. phases (A is K, Rb, Cs and mixtures of these) exhibit superconductivity with a transition temperature that increases with lattice constant8. At higher dopant concentration a body-centred tetragonal A4C60 phase9 and an insulating, body-centred cubic A4C60 phase10 are found. Here we report that the divalent group IIA intercalant calcium can be intercalated into the f.c.c. sites of C60 to form a solid solution, and that, near a Ca:C60 ratio of 5:1, a phase transformation occurs to a simple cubic phase. Measurements of microwave loss, magnetic susceptibility and Meissner effect show that the simple cubic phase becomes superconducting below 8.4 K.

The continuing drive towards miniaturization of electronic devices1 is motivating the search for new materials. Consider, for example, the case of the much-used dynamic random-access memory. The minimum capacitance per cell that can be tolerated is expected2 to remain at 30–40 fF, but as the cell area decreases, the corresponding reduction in geometric capacitance has to be compensated for. So far, this has been achieved by resorting to complex non-planar structures and/or using much thinner films of the dielectric insulator, amorphous silicon dioxide (a-SiOx), although the latter approach is limited by the electric fields that can be supported by a-SiOx before its insulating properties break down. An alternative strategy is to develop thin-film insulators that have a dielectric constant significantly greater than that of a-SiOx, reducing the size of the fields required for device operation. Here we show that a composition-spread technique allows for the efficient evaluating of materials with both a high dielectric constant and a high breakdown field. We apply this approach to the Zr–Sn–Ti–O system, and we find that compositions close to Zr0.15Sn0.3Ti0.55O2−δ are better thin-film dielectrics than high-quality deposited a-SiOx. Although detailed tests of the performance of these materials have not yet been carried out, our initial results suggest that they are likely to be comparable to the best alternatives (such as (Ba, Sr)TiO3) currently being considered for integrated-circuit capacitors.

A WIDE variety of alkali-metal fullerides (AxC60) have been prepared, with stoichiometries varying between 1⩽=x⩽=11 (refs 1,2). Most of the compounds with x = 3 are superconductors with unusually high transition temperatures (Tc) which increase with the size of the face-centred cubic unit cell3. The increase in Tc on lattice expansion is attributed to a decrease in the conduction band width, and therefore one ultimately expects a saturation or downturn of Tc followed by a metal–insulator transition. We have sought to explore this regime by expanding the A3C60 structure through intercalation of neutral molecules capable of solvating the A+ ions. Here we report that the reaction of ammonia with Na2CsC60 (Tc = 10.5K; lattice constant α = 14.132 A) produces the compound (NH3)4Na2CsC60, which has an expanded unit cell (a = 14.473 A) and an increased Tc of 29.6 K. The structure contains the Na(NH3)+4 cation on the octahedral site.

INTERCALATING solid C60 with dopant atoms yields materials with a remarkable range of properties1. Alkali metal atoms, for example, readily form charge-transfer compounds2,3, AxC60 (where A is an alkali metal), which can be metallic, superconducting or insulating depending on the dopant concentration4–9. In all cases, the superconducting phase has a face-centred cubic (f.c.c.) structure and stoichiometry A3C60, which suggests a common mechanism for superconductivity dependent, at least in part, on the external coordination number of the C60 molecules. More recently, it has been shown10 that the alkaline earth metal calcium can also be intercalated with fulleride to form a superconducting phase, again with a f.c.c.-derived structure, near a Ca:C60 ratio of 5:1. Here we report the intercalation of fulleride with barium, in which a pure body-centred cubic phase with a lattice constant of 11.171 A is realized near a stoichiometry of Ba6C60. This phase is also superconducting (with a transition temperature of 7 K), suggesting that the mechanism of superconductivity is related to an intrinsic property of the C60 molecules, rather than the external coordination number.

ALKALI metal fuller ides exhibit superconductivity1–4 at temperatures surpassed only by the copper-oxide-based ceramics. Three types of stoichiometry and structure have been identified: A3C60 (ref. 5) (where A is K or Rb) with A+ cations intercalated in the face-centred cubic (f.c.c.) C60 structure, and A6C60 (ref. 6) or A4C60 (ref. 7) (where A is K, Rb or Cs) with body-centred arrays of C60 molecules. All A3C60 compounds reported so far are superconductors with transition temperatures that increase with unit cell size8,9. No successful preparation of bulk NaxC60 has been reported, although measurements of electrical conductivity10 and Raman11, ESR11 and photoemission12 spectra of thin films have given clear indications of NaxC60 formation. Here we report the synthesis and initial characterization of bulk NaxC60 (2≤x≤6) and mixed alkali phases Na2AC60 (where A is K, Rb, or Cs). All of these phases have intercalated f.c.c. structures. The Na6C60 structure has a Na4 cluster centred on the octahedral site. The Na2AC60 compounds superconduct for the larger A cations, but a crossover to nonsuperconducting behaviour occurs with decreasing cation size and correlates with a minimum in the unit cell volume.

SUPERCONDUCTING K3C60 (ref. 1) has been shown2 to have an intercalated face-centred cubic (f.c.c.) structure, and other A3C60 compounds (where A is K, Rb or mixtures of K, Rb and/or Cs) form an isostructural series with superconducting transition temperatures up to 31.3 K (ref. 3). Recently we reported413C NMR studies of KxC60 for x

THE recent syntheses1,2 of macroscopic quantities of C60 have suggested possible applications in host–guest and organic chemistry, tribology, electrochemistry and semiconductor tech-nology. Here we report the preparation of alkali-metal-doped films of C60 and C70 which have electrical conductivities at room temperature that are comparable to those attained by n-type doped polyacetylene. The highest conductivities observed in the doped films are: 4Scm−1 (Cs/C60), 100 (Rb/C60), 500 (K/C60), 20 (Na/C60), 10 (Li/C60), 2 (K/C70). The doping process is reversed on exposure of the films to the atmosphere. At high doping levels, the films become more resistive. We attribute the conductivity induced in these films to the formation of energy bands from the π orbitals of C60 or C70, which become partially filled with carriers on doping. The smaller alkali metal ions should be able to fit into the interstices in the lattice without disrupting the network of contacts between the carbon spheroids. In the case of C60, this would allow the development of an isotropic band structure, and we therefore propose that these materials may constitute the first three-dimensional 'organic' conductors.

STARTING with the pioneering work of Bednorz and Muller1, many copper-oxide-based superconductors with high transition temperatures (Tc) have been discovered. All contain layers of copper-oxygen squares, pyramids or octahedra as their electronically active structural components2,3. One structure type, first reported for La2SrCu2O6 and La2CaCu2O6 (ref. 4), has stood as an enigma since the beginning of high-Tc research. This crystal structure4-7 (Fig. 1) is the least complex of all the structures with the double layers of copper oxide pyramids common to the compounds with highest Tc, yet despite considerable effort, both published8,9 and unpublished, it has not until now been made superconducting. Here we report the successful synthesis and preliminary physical characterization of superconducting (La, Sr)2CaCu2O6. The highest transition temperature observed is 60 K at the composition La1.6Sr0.4CaCu2O6. This is a uniquely simple double-layer superconductor, which, like its single-layer analogue (La, Sr)2CuO4, becomes superconducting through the introduction of carriers in an unambiguous manner—by straightforward atomic substitution without the intervention of charge reservoir layers with flexible valence states.

THE discovery of conductivity1 in AxC60 (where A represents an alkali metal) and superconductivity2 in KxC60 has been followed by reports of superconductivity in other alkali-metal-doped full-erides with transition temperatures as high as 33 K (ref. 3). Elucidation of phase diagrams and understanding the relationship between structure and superconducting properties is essential to a detailed understanding of superconductivity in these systems. So far, structural data have been reported only for the non-conducting, intercalated body-centred cubic (b.c.c.) structures A6C60 (where A is K or Cs; ref. 4), a body-centred tetragonal structure for A6C60 (where A is K, Rb, Cs; ref. 5) and the superconducting, intercalated face-centred cubic (f.c.c.) material K3C60 (ref. 6). Here we report the preparation of a series of single-phase, isostructural f.c.c. superconductors with composition A3C60 (where A is K, Rb, Cs or a mixture of these), and show that Tcc increases monotonically with the size of the unit cell. Extended Hiickel band-structure calcula-tions also show a monotonic increase in the density of states at the Fermi level, N(EF), with lattice parameter. The primary impli-cation of these results is that all A3C60 superconductors have the same structure and that changes in Tc can be accounted for by changes in N(EF).

Nature 352, 701-703 (1991). THE positions of the alkali atoms, originally reported as (0,0.5, z) with z = 0.28, should read (x,0.5,0) with x = 0.22. These are the positions used in the calculations for Table 1 and the positions illustrated in Fig. 2.

The discovery of superconductivity at temperatures above the boiling point of nitrogen has led to intense interest in the physics and chemistry of materials exhibiting this behaviour. Although some experiments can be performed on sintered polycrystalline samples, large single crystals are important for many measurements of physical properties, including investigations of the relationship between structural parameters and superconducting properties. Like its predecessors YB2Cu3O7 (refs 1–4) and La2–xSrxCuO4 (ref. 5), the recently discovered 84-K bismuth–strontium–calcium cuprate superconductor6–9 melts incon-gruently, and crystals have been grown from eutectic melts10. This technique yields crystals large enough for some experiments, but is generally difficult to control, placing limits on the size of crystals that can be grown. In addition, the crystals must be mechanically separated from the melt. Here we report the growth of single crystals of Bi2.2Sr2Ca0.8Cu2O8+δ from alkali chloride fluxes. The crystals are superconductors, showing large Meissner effects and zero-resistance transitions above 80 K. Flux growth is a standard high-temperature solution growth technique, and should allow crystal size and quality to be controlled by parameters such as equilibration temperature, cooling rate and melt composition. The fluxes reported here are easily washed from the crystals.