Density multiplication of patterned templates by directed self-assembly (DSA) of block copolymers (BCP) stands out as a promising alternative to overcome the limitation of conventional lithography. Using the 300mm pilot line available in LETI and Arkema’s materials, the main objective is to integrate DSA directly into the conventional CMOS lithography process in order to achieve high resolution and pattern density multiplication at a low cost. Thus we investigate the potential of DSA to address contact and via level patterning by performing either CD shrink or contact multiplication. Our approach is based on the graphoepitaxy of PS-b-PMMA block copolymers. Lithographic performances of block copolymers are evaluated both for contact shrink and contact doubling. Furthermore, advanced characterization technics are used to monitor in-film self-assembly process. These results show that DSA has a high potential to be integrated directly into the conventional CMOS lithography process in order to achieve high resolution contact holes.

Semi-conducting conjugated (co)polymers are well soluble and can be processed easily in a large scale. Among these materials, rod-coil block and graft copolymers, show very particular properties of self-assembly, and are very promising in organic electronic, as organic photovoltaic materials for example.

The post-functionalization of poly(3-hexylthiophene) (P3HT) from ω-allyl terminated P3HT via various synthetic routes is reported in order to obtain well-defined block and graft copolymers for optoelectronic or photovoltaic applications. First, a well-defined and monofunctional P3HT-based macro-initiator has been obtained through a clean and versatile process. Well-defined rod-coil block copolymers were obtained by nitroxide mediated radical polymerization (NMRP) with various monomers. Finally, three different novel P3HT-based graft copolymers were synthesized following two routes.

This article focuses on self-assembled photovoltaic materials based on a new class of semiconducting block copolymers for application in photovoltaic devices. Topics discussed include the materials concept for efficient photovoltaic-device structures, their macromolecular design and synthesis, and their performance in relation to their molecular, mesoscopic, and interfacial structures. An ideal organic material for this application would have to compete with amorphous silicon in regard to energy-conversion efficiency and fabrication costs. The potential of the semiconducting block copolymers presented in this review lies in the promise of large-area, mechanically flexible, self-structured photovoltaic devices fabricated by inexpensive processing techniques.

Asymmetrically substituted oligo(phenylene ethynylene) (OPE) derivatives have been prepared by a new iterative method and attached to C60 molecules by a 1,3-dipolar cycloaddition of the azomethine ylides generated in situ from the corresponding aldehydes and sarcosine. The molecules obtained are suitable for the fabrication of photovoltaic devices based on interpenetrating networks of donors and acceptors, with a characteristic length scale of the network topology smaller than the exciton diffusion length. We have constructed a number of photovoltaic cells incorporating the C60-OPEs as the active material between two energetically asymmetric electrode contacts. The device performance has been examined and the functional characteristics have been determined too. These seem to depend systematically on the nature of the attached end-group and on the length of the donating moiety.

We report neutron reflectivity data on (poly)styrene-(poly)ethylene oxide (PS-PEO) diblock copolymers adsorbed onto quartz from the selective solvent deuterated cyclohexane (a non-solvent for PEO and a poor solvent for PS). The PEO "anchor block" adsorbs strongly to form a thin layer on the quartz substrate, while the PS chains dangle into the solvent. We find that under static conditions the density profile of the PS block in a poor solvent can be well described by a Schultz function which is indicative of a polymer "mushroom." Furthermore, we have studied the same system under shear at shear rates from 0-400s-l. We find that there is a dramatic increase in the thickness of the PS layer under shear in cyclohexane and that the relaxation time from the shear-on profile back to the static profile is on the order of several days.