Solid state physicochemical properties and applications of organic and metallo-organic fullerene derivatives

We review the fundamental properties and main applications of organic derivatives and complexes of fullerenes in the solid-state form. We address in particular the structural properties, in terms of crystal structure, polymorphism, orientational transitions and morphology, and the electronic structure and derived properties, such as chemical activity, electrical conduction mechanisms, optical properties, heat conduction and magnetism. The last two sections of the review focus on the solid-state optoelectronic and electrochemical applications of fullerene derivatives, which range from photovoltaic cells to field-effect transistors and photodetectors on one hand, to electron-beam resists, electrolytes and energy storage on the other.Peer ReviewedPreprin

Order-disorder transition and alignment dynamics of a block copolymer under high magnetic fields by in situ x-ray scattering

We present results of temperature resolved scattering studies of a liquid crystalline block copolymer undergoing an order-disorder transition (ODT) in the presence of magnetic fields and time-resolved measurements during isothermal field annealing at sub-ODT temperatures. In each case, field interactions produced strongly textured mesophases with the cylindrical microdomains aligned parallel to the field. We find there is no measurable field-induced shift in the ODT temperature ($T_{ODT}$) which suggests that selective melting does not play a role in mesophase alignment during isothermal experiments. Our data indicate instead that sub-ODT alignment occurs by slow, large scale grain rotation whereas alignment during cooling from the disordered melt is rapid and driven by the nucleation of weakly ordered but preferentially aligned material. We identify an optimum sub-cooling that maximizes alignment during isothermal field annealing. This is corroborated by a simple model incorporating the competing effects of an exponentially decreasing mobility and divergent, increasing magnetic anisotropy on cooling below $T_{ODT}$. The absence of measurable field-effects on $T_{ODT}$ is consistent with rough estimates derived from the relative magnitudes of the free energy due to field interaction and the enthalpy of the isotropic-LC transition.Comment: 5 figures; To appear in Physical Review Letter

Strong orientational coupling of block copolymer microdomains to smectic layering revealed by magnetic field alignment

We elucidate the roles of the isotropic-nematic (I-N) and nematic-smectic A (N-SmA) transitions in magnetic field directed self-assembly of a liquid crystalline block copolymer (BCP), using \textit{in situ} x-ray scattering. Cooling into the nematic from the disordered melt yields poorly ordered and weakly aligned BCP microdomains. Continued cooling into the SmA however results in an abrupt increase in BCP orientational order with microdomain alignment tightly coupled to the translational order parameter of the smectic layers. These results underscore the significance of the N-SmA transition in generating highly aligned states under magnetic fields in these hierarchically ordered materials

The Need for PFC Abatement in Semiconductor Manufacturing

Perfluorocompounds (PFCs) are highly stable chemical compounds used in two integral steps of semiconductor manufacturing: chemical vapor deposition (CVD) chambers and etch chambers. Unfortunately, PFCs are also greenhouse gases linked to global warming. This, combined with their long atmospheric lifetimes gives them global warming potentials much higher than C02 the principal greenhouse gas. In a series of voluntary agreements with the United States and other national governments, the worldwide semiconductor industry has set a goal of reducing PFC emissions to 90% of their 1995 levels. To reach this goal, researchers have explored four main methods of reduction: substitution of PFCs, recovery and recycling of PFCs, tool optimization, and exhaust abatement. While the first three methods have successfully reduced emissions in the CVD chambers, they have proven too costly for or inapplicable to etch chambers. Therefore, it has become apparent that further reductions must be achieved through the abatement of etch chamber exhaust. Herein, we compare three commercially available abatement systems representative of the three techniques currently used to abate PFCs. All three systems are categorized as either downstream systems, which receive diluted exhaust from multiple etch chambers, or point-of-use (POU) systems, which receive concentrated exhaust from a single etch chamber. Though both downstream and POU configurations are equally effective in destroying PFCs, they differ in cost depending on the number of etch chambers in use and the dilution rate per chamber. Given these numbers, our Microsoft Excel-based cost model computes the total cost of each of the three commercial systems, allowing the user to determine which system is most economical for a specific factory setting

Conformational instability of human prion protein upon residue modification: a molecular dynamics simulation study

Technical strategies like amino acid substitution and residue modification have been widely used to characterize the importance of key amino acids and the role that each residue plays in the structural and functional properties of protein molecules. However, there is no systematic approach to assess the impact of the substituted/modified amino acids on the conformational dynamics of proteins. In this investigation to clarify the effects of residue modifications on the structural dynamics of human prion protein (PrP), a comparative molecular dynamics simulation study on the native and the amino acid-substituted analog at position 208 of PrP has been performed. It is believed that Arginine to Histidine mutation at position 208 is responsible for the structural transition of the native form of human prion protein to the pathogenic isoform causing Creutzfeldt-Jakob disease (CJD). So, three 10 ns molecular dynamics simulations on three model constructs have been performed. Simulation results indicated considerable differences of conformational fluctuations for Alanine substituted construct (PrPALA) and the analog form (PrPSB) comprising the neutralized state of the Arginine residue at position 208 of the human prion protein. According to our data, substitution of the Arginine residue by the uncharged state of this residue induces some reversible structural alterations in the intrinsically flexible loop area including residues 167–171 of PrP. Thus, deprotonation of Arg208 is a weak perturbation to the structural fluctuations of the protein backbone and the resulting construct behaves almost identical as its native form. Otherwise, Alanine substitution at position 208 imposed an irreversible impact on the secondary and tertiary structure of the protein, which leads to conformational instabilities in the remote hot region comprising residues 190–195 of the C–terminal part of helix 2. Based on the results, it could be deduced that the observed conformational transitions upon Arg208 to His point mutation, which is the main reason for CJD, may be mainly related to the structural instabilities due to the induced-conformational changes that caused alterations in local/spatial arrangements of the force distributions in the backbone of the human prion protein