Silver oligomer and single fullerene electronic properties revealed by a scanning tunnelling microscope

Clusters on surfaces have been investigated with low-temperature scanning tunnelling microscopy and spectroscopy. Constant current spectra acquired on Ag oligomers and one-dimensional chains on a Ag(111) reveal a single resonance peak whose energy shifts towards the Fermi level with increasing cluster size. Next, controlled and reproducible contact between a STM tip and a C₆₀ molecule adsorbed on Cu(100) is reported. The transition from tunnelling to contact is discussed in terms of local heating of the tip-molecule junction.     

Metastable surface phase for NaxC60

Na_xC₆₀ thin films with Na concentration 0 ? x ? 3 were investigated using angle-dependent photoelectron spectroscopy. For low doping we observed two distinct fulleride phases coexisting with regions of pristine C₆₀. One of these fulleride phase is predominantly formed close to the surface and disappears after annealing and further addition of Na. At higher doping a phase with stoichiometry of x = 3 is formed.     

Concentric Sub‐micrometer‐Sized Cables Composed of Ni Nanowires and Sub‐micrometer‐Sized Fullerene Tubes

Highly ordered arrays of submicrometer‐sized coaxial cables composed of submicrometer‐sized C₆₀ and C₇₀ tubes filled with Ni nanowires are successfully prepared by combining a sol–gel method with an electrodeposition process. The wall thickness of the submicrometer‐sized tubes can be adjusted by the concentration of fullerenes and the immersion time. The thermal stability of the submicrometer‐sized C₆₀ tubes is studied by Raman spectroscopy and it is found that these structures can be easily decomposed to form carbon nanotubes at relatively low temperatures (above 573 K) in an alumina template. These novel coaxial cable structures have been characterized by transmission electron microscopy (TEM), high‐resolution TEM (HRTEM), scanning electron microscopy (SEM), field‐emission SEM (FESEM), Raman spectroscopy, elemental mapping, energy dispersive X‐ray (EDX) spectroscopy, X‐ray diffraction (XRD), vibrating sample magnetometer (VSM) experiments, and superconducting quantum interference device (SQUID) measurements. Magnetic measurements show that these submicrometer‐sized cables exhibit enhanced ferromagnetic behavior as compared to bulk nickel. Moreover, submicrometer‐sized C₇₀/Ni cables show uniaxial magnetic anisotropy with the easy magnetic axis being parallel to the long axis of the Ni nanowires. C₇₀/Ni cables also exhibit a new magnetic transition at ca. 10 K in the magnetization–temperature (M–T) curve, which is not observed for the analogous C₆₀/Ni structures. The origin of this transition is not yet clear, but might be related to interactions between the Ni nanowires and C₇₀ molecules. There is no preferred magnetization axis in submicrometer‐sized C₆₀/Ni cables, which implies that the Ni nanocrystals have different packing modes in the two composites. These different crystalline packing modes lead to different magnetic anisotropy in the two composites, although the Ni nanocrystals have the same face‐centered cubic (fcc) structure in both cases.     

Organic Thin‐Film Photovoltaic Cells Based on Oligothiophenes with Reduced Bandgap

The best polymeric solar cells reported so far are based on a so‐called bulk heterojunction of a polythiophene as donor and a soluble fullerene derivative as acceptor. However, these cells still suffer from an unsatisfying photovoltage, typically below 0.7 V. Here, we show that we can achieve higher photovoltages using a new terthiophene end‐capped with electron withdrawing dicyanovinyl groups (DCV3T) that increase both the ionization energy and even more strongly the electron affinity of the compound. The new material is tested in cells using a photoactive heterojunction to separate the excitons generated in the oligomer and a p‐doped wide‐gap transport layer. The solar cells show an open circuit voltage of up to 1.04 V and a broad spectral sensitivity band ranging from 420 nm to 650 nm. Solar cells based on such oligothiophenes are promising candidates for stacked organic solar cells tailored to the sun‐spectrum. Moreover, we present first examples of a new concept for organic solar cells: By blending DCV3T with fullerene C₆₀, an enhanced generation of triplet excitons on the oligomer can be achieved via a back and forth transfer of excitons (ping‐pong‐effect).     

Computer-aided design of nanostructured materials containing trisaza-bridged [60]fullerene

A novel fullerene-based building block for the synthesis of nanostructured materials has been designed with the aid of electronic structure theory calculations and molecular modeling. The building block consists of four trisaza-bridged C₆₀ fullerene molecules linked to a central cubane (C₈) unit. Each C₆₀ unit is located on the vertex of a tetrahedron with edge of 2.2 nm. One possible packing mode of the building blocks to yield the nanostructured material is suggested.     

Prediction of thermodynamic properties from pure compound information: Characterization of fullerenes

Fullerenes are widely studied not only in material, but also in life science due to their special properties. Their surface properties determine their interaction with the environment and influence adsorption as well as biodistribution. In this work, the surfaces of a series of fullerenes and polyhydroxylated C₆₀-fullerenes were investigated using density functional theory (DFT)/conductor-like screening model (COSMO)-calculations. The dependence of the screening charge density from the curvature of a carbon hexagon and its effect on the adsorption behavior was studied. The estimation of thermodynamic properties of multiply functionalized C₆₀-molecules gives promising qualitative results using only properties of the pure compounds.     

Nonlinear optical properties of C<Subscript>60</Subscript> with explicit time-dependent electron dynamics

An explicit electron dynamics approach has been used to calculate the nonlinear optical properties of C₆₀ and its radical anion. An external perturbation, in the form of an oscillating electric field, induces the time-evolution of the molecular wavefunction. The time-averaged instantaneous dipole moment of the systems gives the molecular response to perturbations of varying field intensities and frequency of oscillation. The polarizabilities and the second-order hyperpolarizabilties have been calculated and are in good qualitative agreement with experimentally available data. In line with previous theoretical and experimental studies, the nonlinear effect is enhanced for the radical species. Contribution to the Fernando Bernardi Memorial Issue.     

A step toward direct fullerene synthesis: C60 fullerene precursors with fluorine in key positions

Several fluorine containing polycyclic aromatic hydrocarbons with exact carbon atom topology of the C₆₀ fullerene have been synthesized. Different numbers of fluorine atoms were introduced in the key positions, as needed for an efficient intramolecular condensation to the fullerene molecule. The polycyclic aromatic compounds obtained represent attractive precursors for rational, high-yield fullerene synthesis by flash vacuum pyrolysis.     

An oxacalix[2]arene[2]pyrimidine-bis(Zn-porphyrin) tweezer as a selective receptor towards fullerene C70

An oxacalix[2]arene[2]pyrimidine-bis(Zn^II-porphyrin) conjugate was readily prepared via nucleophilic aromatic substitution of a phenolic AB₃-Zn-porphyrin on the upper rim of a (1,3-alternate) 5,17-bis(methylsulfonyl)oxacalix[4]arene precursor. Efficient 1:1 complex formation between the ‘jaws’ bisporphyrin tweezer and fullerene C₇₀ was evidenced by ¹H NMR titrations (K = 3.0 × 10⁴ M⁻¹), while no detectable complexation could be observed with C₆₀. On the other hand, an analogous oxacalix[4]arene-bis(Cu-corrole) conjugate did not show any measurable (C₆₀ or C₇₀) fullerene binding.     

Measuring the External Quantum Efficiency of Two‐Terminal Polymer Tandem Solar Cells

Tandem configurations, in which two cells are stacked and connected in series, offer a viable approach to further increase the power conversion efficiency (PCE) of organic solar cells. To enable the future rational design of new materials it is important to accurately assess the contributions of individual subcells. Such accurate measurement of the external quantum efficiency (EQE) of the subcells of two‐terminal organic or polymer tandem solar cells poses specific challenges, caused by two characteristics of these cells, i.e. a sub‐linear light intensity dependence of the current and a field‐assisted charge collection. These properties necessitate that EQE experiments are carried out under representative illumination conditions and electrical bias to maintain short‐circuit conditions for the addressed subcell. We describe a method to determine the magnitudes of the bias illumination and bias voltage during EQE measurements, based on the behavior of single junction cells and optical modeling. The short‐circuit current densities of the subcells obtained by convolution of the EQE with the AM1.5G solar spectrum are consistent with those obtained from optical modeling and correctly predict the current density–voltage characteristics of the tandem cell under AM1.5G conditions.