Tuning the Dimensions of C60‐Based Needlelike Crystals in Blended Thin Films

A new ordered structure of the C₆₀ derivative PCBM ([6‐6]‐phenyl C₆₁‐butyric acid methyl ester) is obtained in thin films based on the blend PCBM:regioregular P3HT (poly(3‐hexylthiophene)). Rapid formation of needlelike crystalline PCBM structures of a few micrometers up to 100 μm in size is demonstrated by submitting the blended thin films to an appropriate thermal treatment. These structures can grow out to a 2D network of PCBM needles and, in specific cases, to spectacular PCBM fans. Key parameters to tune the dimensions and spatial distribution of the PCBM needles are blend ratio and annealing conditions. The as‐obtained blended films and crystals are probed using atomic force microscopy, transmission electron microscopy, selected area electron diffraction, optical microscopy, and confocal fluorescence microscopy. Based on the analytical results, the growth mechanism of the PCBM structures within the film is described in terms of diffusion of PCBM towards the PCBM crystals, leaving highly crystalline P3HT behind in the surrounding matrix.     

Synthesis of 2,7‐Carbazolenevinylene‐Based Copolymers and Characterization of Their Photovoltaic Properties

New electroactive and photoactive conjugated copolymers consisting of alternating 2,7‐carbazole and oligothiophene moieties linked by vinylene groups have been developed. Different oligothiophene units have been introduced to study the relationship between the polymer structure and the electronic properties. The resulting copolymers are characterized by UV‐vis spectroscopy, size‐exclusion chromatography, and thermal and electrochemical analyses. Bulk heterojunction photovoltaic cells from different copolymers and a soluble fullerene derivative, [6,6]‐phenyl‐C₆₁ butyric acid methyl ester, have been fabricated, and promising preliminary results are obtained. For instance, non‐optimized devices using poly(N‐(4‐octyloxyphenyl)‐2,7‐carbazolenevinylene‐alt‐3″,4″‐dihexyl‐2,2′;5′,2″;5″,2″′;5″′,2″″‐quinquethiophenevinylene 1″,1″‐dioxide) as an absorbing and hole‐carrier semiconductor exhibit power conversion efficiency up to 0.8 % under air mass (AM) 1.5 illumination. These features make 2,7‐carbazolenevinylene‐based and related polymers attractive candidates for solar‐cell applications.     

Synthesis and Evaluation of Blends Formed by Polymeric Crown Ethers and a Fullerene-Containing Primary Ammonium Salt in Organic Thin Films

The synthesis of a series of polymers and cyclopolymers bearing crown ethers of differing structure and affinities towards primary ammonium ions is discussed. These polymers have been tested in their efficiency to form structurally homogeneous thin films when blended with an amphiphilic C₆₀ compound containing a primary ammonium ion functional group. The X-ray reflectivity characterization of the films revealed that the polymer bearing the crown ether with the least affinity for primary ammonium ions, but having the highest degree of polymerization, is the most effective in forming structurally homogeneous thin films.     

Relating the Morphology of Poly(p‐phenylene vinylene)/Methanofullerene Blends to Solar‐Cell Performance

The performance of bulk‐heterojunction solar cells based on a phase‐separated mixture of donor and acceptor materials is known to be critically dependent on the morphology of the active layer. Here we use a combination of techniques to resolve the morphology of spin cast films of poly(p‐phenylene vinylene)/methanofullerene blends in three dimensions on a nanometer scale and relate the results to the performance of the corresponding solar cells. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and depth profiling using dynamic time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) clearly show that for the two materials used in this study, 1‐(3‐methoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐methanofullerene (PCBM) and poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV), phase separation is not observed up to 50 wt.‐% PCBM. Nanoscale phase separation throughout the film sets in for concentrations of more than 67 wt.‐% PCBM, to give domains of rather pure PCBM in a homogenous matrix of 50:50 wt.‐% MDMO‐PPV/PCBM. Electrical characterization, under illumination and in the dark, of the corresponding photovoltaic devices revealed a strong increase of power conversion efficiency when the phase‐separated network develops, with a sharp increase of the photocurrent and fill factor between 50 and 67 wt.‐% PCBM. As the phase separation sets in, enhanced electron transport and a reduction of bimolecular charge recombination provide the conditions for improved performance. The results are interpreted in terms of a model that proposes a hierarchical build up of two cooperative interpenetrating networks at different length scales.     

Young’s modulus of crystalline C60 nanotubes studied by in situ transmission electron microscopy

Bending tests of crystalline nanotubes composed of fullerene C₆₀ molecules are performed inside a high-resolution transmission electron microscope. We fixed one side of a C₆₀ nanotube with a body-centered tetragonal structure with typical inner and outer diameters, i.e., 180 nm and 510 nm, respectively, and then applied concentrated forces on the other side using piezomanipulation of a silicon nanotip. The bending process was observed in situ by transmission electron microscopy with simultaneous measurements of the forces by an optical deflection method. It was found that the Young’s modulus of the nanotube was estimated to be 62–107 GPa, which was 1.1–3.3 times larger than that of C₆₀ nanowhiskers. The result concerning the increase in the Young’s modulus of the C₆₀ nanotube provided an experimental evidence for the structural model composed of an inner core and a surface shell for C₆₀ nanowhiskers.     

Studies on Preparation of Onion-like Fullerenes by Vacuum Heat-treatment

Onion-like Fullerenes were produced at high-temperature in vacuum. The morphology of the carbon nano onion-like fullerenes was examined and characterized by high-resolution transmission electron microscopy (HRTEM). It can be seen that the nano-sized, onion-like fullerenes possess high degree of graphization. The results suggested that the catalyst is the main factor affecting the size and yield of the fullerenes. The method is very promising for simple mass production.     

Induction plasma synthesis of fullerenes and nanotubes using carbon black–nickel particles

The existence of fullerenes (as allotropes of carbon) was established in the mid-1980s and during the last 15–18 years, systematic efforts have been devoted to improve the methods of their synthesis, including plasma-based system methods. The work presented here is focused on the investigation of fullerenes synthesis, using a radio frequency plasma reactor. The main objectives were to explore the use of induction plasma technology for the synthesis in-continuo of carbon fullerenes and to predict their formation conditions through conduct of theoretical studies. Thus, a thermodynamic study was carried out to predict the equilibrium composition of fullerenes produced at several combinations of operating conditions. Additionally, a statistical factorial design experiment, employing four factors at two levels, was also developed, in order to study the influence of the system’s operating parameters on the eventual C₆₀ fullerene yield. The results obtained showed that the reactor pressure, the electrical power and the raw material feed rates all have an important effect on the synthesis of fullerenes. The highest C₆₀ concentration in the products was found to be about 7.7 wt.%. Various other carbon nanostructures, such as nanotubes and nano-onions, were also successfully produced.     

Molecular beam studies of fullerenes

A number of molecular beam experiments with the fullerenes are described. Such experiments allow a detailed probing of the interactions between fullerenes and other species and among the fullerenes themselves. Emphasis is placed on work involving photophysics and collisional interactions of the fullerenes.     

Effects of fullerenes and single-wall carbon nanotubes on murine and human macrophages

The discovery in 1985 of C-fullerenes, a novel carbon allotrope with a polygonal structure made up solely by 60 carbon atoms, and in 1991 of C-nanotubes, thin carbon filaments (1-3 μm in length and 0.001 μm in diameter) with extraordinary mechanical properties, opened a wide field of activity in carbon research. While toxicity and biocompatibility of C-fullerenes have been widely investigated, literature data concerning the biological properties and biotoxicity of C-nanotubes are poor and contradictory. Here we test the ability of highly purified C-Single-Walled-Nanotubes (SWNTs) and C-fullerenes to elicit an inflammatory response by murine and human macrophage cells in vitro. In order to determine the potential of these C-derivatives as biological inducers of inflammatory reactions we evaluate the ability of C-single-walled nanotubes and C-fullerenes to induce the release of NO by murine macrophages cells, to stimulate the phagocytic activity of human macrophage cells and to be cytotoxic against these cells. We show that SWNTs-C-nanotubes, when highly purified, as well as C-fullerenes, do not stimulate the release of NO by murine macrophage cells in culture, their uptake by human macrophage cells is very low, and they possess a very low toxicity against human macrophage cells.     

Orbital pairing effects in fullerenes

We propose a theory of superconductivity for a crystal having multiple band structure. The theory is valid for the parameter(k _F)/1 when the splitting between bands(k _F ) is small in comparison with the phonon frequency. The theory may be applicable to the doped fullerenes where it is widely supposed that pairing occurs through high-energy intramolecular phonons. As in semiconductors, the bunch of bands is treated by ascribing the highest spin to electrons. We derive the analytic expression for the critical temperature, which strongly depends on the value of the total spin of the Cooper pair, which may be equal toY=0,1,.... In all cases the order parameter is a vector with components proportional to spherical harmonics and at the same time the superconducting gap has no zeros. The data may be fitted to doped fullerenes, if the superconductivity arises fromd-pairing.