ON THE MECHANISM OF CARBON CLUSTERS FORMATION UNDER LASER IRRADIATION. THE CASE OF DIAMOND GRAINS AND SOLID C60 FULLERENE

ABSTRACT

It is shown by FT-ICR (Fourier transform ion cyclotron resonance) mass spectrometry that carbon clusters considered to be the superior homologues of C₆₀ fullerene are formed by laser irradiation of both synthetic diamond grains or from pure C₆₀ fullerene crystals. The surfaces of the laser irradiated diamond or C₆₀ have been examined by Raman spectroscopy. In the case of diamond the Raman spectrum suggests the superficial formation of mixed carbon nanostructures consisting of disordered graphite, fullerenic nanostructures, onion-like carbon nanostructures and diamond-like carbon. Based on the Raman spectra of the surface and on data taken from the phase diagram of carbon, it is shown that the graphitization is needed in order to produce fullerenes from diamond under laser ablation conditions. In the case of C₆₀ fullerene, it is shown by Raman spectroscopy that the laser irradiation of the crystals causes initially their photopolymerization and after further irradiation their transformation into disordered graphite. Based on these results and on a literature survey on the formation of fullerenes from more than 15 completely different substrates, it is concluded that fullerenes are formed always when laser ablation leads to a graphitization of the laser-irradiated substrate. Some astrochemical implications of the conclusions have been discussed.     

Structural and Vibrational Properties of Li‐ and Na‐Doped Fullerene Polymers

Abstract

We have studied tetragonal C₆₀ and C₆₀‐based polymers doped with Lithium and Sodium. We show that the intercalated phases Li₄C₆₀ and Na₄C₆₀ both form two‐dimensional polymers. X‐ray diffraction diagrams for Li₄C₆₀ and tetragonal C₆₀ can be accurately indexed assuming tetragonal structures, but for Na₄C₆₀ a monoclinic quasi‐tetragonal structure is found. We conclude that in Li₄C₆₀ the covalent bonds are formed by (2 + 2) cycloadditions, in the same way as in the tetragonal polymer produced by treating pure C₆₀ at high temperature and high pressure, while single C–C bonds connect the fullerene molecules in Na₄C₆₀.     

HPLC Diode‐Array Analysis of C60 and C70 Polymeric Fullerene Oxides (Fullerene Polymeric Ozonides)

Abstract

It is shown by HPLC diode‐array analysis that the C₆₀ and C₇₀ polymeric fullerene oxides ([C₆₀]‐PFOs and [C₇₀]‐PFOs) which are polymeric ozonides, are composed by nine different components. The ozonide derivatives of C₆₀ and C₇₀ have been proved to be practically analogous in chemical structure and composition. The most important component of both [C₆₀]‐PFOs and [C₇₀]‐PFOs accounts for about 3/4 of each sample. The overozonation of [C₆₀]‐PFOs in methanol has been studied and shown to not produce any significant changes.     

Conjugated Polymer Based on Polycyclic Aromatics for Bulk Heterojunction Organic Solar Cells: A Case Study of Quadrathienonaphthalene Polymers with 2% Efficiency

Polycyclic aromatics offer great flexibility in tuning the energy levels and bandgaps of resulting conjugated polymers. These features have been exploited in the recent examples of benzo[2,1‐b:3,4‐b']dithiophene ( BDT )‐based polymers for bulk heterojunction (BHJ) photovoltaics (ACS Appl. Mater. Interfaces 2009 , 1, 1613). Taking one step further, a simple oxidative photocyclization is used here to convert the BDT with two pendent thiophene units into an enlarged planar polycyclic aromatic ring— q uadra t hieno n aphthalene ( QTN ). The reduced steric hindrance and more planar structure promotes the intermolecular interaction of QTN‐ based polymers, leading to increased hole mobility in related polymers. As‐synthesized homopolymer ( HMPQTN ) and donor–acceptor polymer ( PQTN ‐ BT ) maintain a low highest occupied molecular orbital (HOMO) energy level, ascribable to the polycyclic aromatic ( QTN ) moiety, which leads to a good open‐circuit voltage in BHJ devices of these polymers blended with PCBM ([6,6]‐phenyl‐C₆₁‐butyric acid methyl ester; HMPQTN : 0.76 V, PQTN ‐ BT : 0.72 V). The donor–acceptor polymer ( PQTN ‐ BT ) has a smaller optical bandgap (1.6 eV) than that of HMPQTN (2.0 eV), which explains its current (5.69 mA cm^?2) being slightly higher than that of HMPQTN (5.02 mA cm^?2). Overall efficiencies over 2% are achieved for BHJ devices fabricated from either polymer with PCBM as the acceptor.     

Fe3O4 nanoparticles induced magnetic field effect on efficiency enhancement of P3HT:PCBM bulk heterojunction polymer solar cells

Fe₃O₄ magnetic nanoparticles (mean size of about 10 nm) capped by surfactant oleic acid (OA) were incorporated into P3HT:PCBM BHJ-PSCs by doping in the P3HT:PCBM photoactive layer for the first time. The PCE of the OA-Fe₃O₄:P3HT:PCBM BHJ-PSC device is enhanced by ∼18% at the optimum OA-Fe₃O₄ NPs doping ratio of 1%. The role of the magnetic property of Fe₃O₄ NPs on the PCE of OA-Fe₃O₄:P3HT:PCBM devices was studied, confirming the exclusive contribution of the Fe₃O₄ NPs to the observed enhancement of PCE. The enhancement of the PCE of the OA-Fe₃O₄:P3HT:PCBM BHJ-PSC device is found to be primarily due to the increase of short-circuit current (J_sc) by ∼14%, which is attributed to the magnetic field effect originated from the superparamagnetism of Fe₃O₄ NPs, resulting in the increase of the population of triplet excitons. Finally, the effect of Fe₃O₄ NPs on the enhancement of PCE of OA-Fe₃O₄:P3HT:PCBM device is further investigated by comparing different means of doping in P3HT:PCBM or PEDOT:PSS layer, confirming that such an effect can be achieved only when Fe₃O₄ NPs are doped in the P3HT:PCBM photoactive layer.     

Synthesis and properties of a new [60] fullerene-donor system containing dicyanovinyl groups

C₆₀ covalently connected with dicyanovinyl functionalized tris[4-(2-thienyl)phenyl]amine [C₆₀-TTPA(DCV)] (compound 1) has been successfully prepared and it was found to exhibit excellent solubility in common organic solvents with a broad visible-light harvest. The theoretical calculation of its molecular geometry and electronic structure indicates that the TTPA(DCV) moiety and C₆₀ part are acting as donor and acceptor respectively; By comparing with the UV-visible absorption spectra of amine 2, the slight red shift of compound 1 could explain the existence of a small portion of charge transport between the two parts; and the fluorescence spectra of compound 1 show that the intramolecular photo-induced electron transfer from the TTPA(DCV) to C₆₀ is the main pathway for the emission quenching.     

Fast ion collisions with C60 in vapour phase and collective excitation: Comparison with other gaseous targets

The single and double ionization of a free C₆₀ molecule in collisions with fast heavy (F and Si) ions is investigated using a recoil ion time-of-flight mass spectrometer. The projectile charge state (q_p) dependence has also been investigated. A linear q_p-dependence has been explained in terms of a plasmon excitation model. In addition, continuum electron spectroscopy has been used to detect the electron emission from fullerenes. The measured electron angular distribution for the fullerene target is compared with that for a gaseous target at a fixed electron energy. The ratio of forward-to-backward cross section for C₆₀ is quite different from that for Ne.     

ON THE MECHANISM OF CARBON CLUSTERS FORMATION UNDER LASER IRRADIATION. THE CASE OF DIAMOND GRAINS AND SOLID C60 FULLERENE

It is shown by FT-ICR (Fourier transform ion cyclotron resonance) mass spectrometry that carbon clusters considered to be the superior homologues of C₆₀ fullerene are formed by laser irradiation of both synthetic diamond grains or from pure C₆₀ fullerene crystals. The surfaces of the laser irradiated diamond or C₆₀ have been examined by Raman spectroscopy. In the case of diamond the Raman spectrum suggests the superficial formation of mixed carbon nanostructures consisting of disordered graphite, fullerenic nanostructures, onion-like carbon nanostructures and diamond-like carbon. Based on the Raman spectra of the surface and on data taken from the phase diagram of carbon, it is shown that the graphitization is needed in order to produce fullerenes from diamond under laser ablation conditions. In the case of C₆₀ fullerene, it is shown by Raman spectroscopy that the laser irradiation of the crystals causes initially their photopolymerization and after further irradiation their transformation into disordered graphite. Based on these results and on a literature survey on the formation of fullerenes from more than 15 completely different substrates, it is concluded that fullerenes are formed always when laser ablation leads to a graphitization of the laser-irradiated substrate. Some astrochemical implications of the conclusions have been discussed.