This Perspective addresses the current state of block copolymer lithography and identifies key challenges and opportunities within the field. Significant strides in experimental and theoretical thin film research have nucleated the transition of block copolymers “from lab to fab”, but outstanding questions remain about the optimal materials, processes, and analytical techniques for first-generation devices and beyond. Particular attention herein is focused on advances and issues related to thermal annealing. Block copolymers are poised to change the traditional lithographic resolution enhancement paradigm from “top-down” to “bottom-up”.

An organically modified montmorillonite was compounded with ethylene vinyl acetate copolymer (EVA), low density polyethylene (LDPE), and high density polyethylene (HDPE) in a twin‐screw extruder. The resulting organoclay‐polyethylene nanocomposites were then blown into films. Tensile properties and oxygen permeability of these nanocomposite films were investigated to understand the effects of organoclay on different types of polyethylene. It was found that the clay enhancing effects are function of the matrix. The mechanical and oxygen barrier properties of clay/EVA systems increased with clay loading. Both the tensile modulus and oxygen barrier of EVA doubled at 5 wt% clay. Maleic anhydride grafted polyethylene (MAPE) usually is used as a compatibilizer for LDPE and HDPE‐based nanocomposites. However, the MAPEs were found to weaken the oxygen barrier of the PEs, especially for HDPE. This is believed to be a result of less compactness caused by the large side groups and the increase in polarity of the MAPEs. Incorporating 5 wt% clay improves the oxygen barrier by 30% and the tensile modulus by 37% for the LDPE/MAPE system. Incorporation of clay does not enhance the properties of the HDPE‐based systems, likely due to large domain structure and poor bonding. Halpin–Tsai equation and the tortuous path equation were used to model the tensile modulus and oxygen permeability of the clay/EVA nanocomposite films. POLYM. ENG. SCI., 47:1101–1107, 2007. © 2007 Society of Plastics Engineers

Polystyrene (PS) that has been exposed to ultraviolet light (UV) undergoes partial dehydrogenation of the alkane polymer backbone which increases its surface energy. Exploiting this photochemistry, we exposed polystyrene films to UV light using a photomask to induce a patterned photochemical reaction producing regions in the film with differing surface energy. Upon heating the solid polymer film with the preprogrammed surface energy pattern to a liquid state, the polymer flows from the low surface energy unexposed regions to high surface energy exposed regions. This flow creates three-dimensional topography by the Marangoni Effect, which describes convective mass transfer due to surface energy gradients. The topographical features can be permanently preserved by quenching the film below its glass to liquid transition temperature. Their shape and organization are only limited by the pattern on the photomask.

Nanoparticles embedded in a polymeric matrix produce polymer "nanocomposites" (PNCs) which can exhibit unique properties. 1,2 The early literature on nylon PNCs provides a good example. Dramatic alteration of the mechanical properties, thermal stability, and gas barrier characteristics result from the addition of relatively small amounts (2À6 wt %) of montmorillonite clay. 3,4 At least some of the property enhancements unique to PNCs are due to alteration of the matrix material near the nanoparticle surface, which can contribute importantly since the internal surface area in PNCs is very large relative to composites made with micrometer-sized filler (a factor of 10 2 À10 3 larger). Consider, for example, a PNC with monodisperse spherical nanoparticles of diameter d and volume fraction φ P . If there exists an altered interfacial layer of thickness δ surrounding each nanoparticle, then the volume fraction of interfacial material in the matrix, φ δ , is given by

A Marangoni flow is shown to occur when a polymer film possessing a spatially-defined surface energy pattern is heated above its glass transition to the liquid state. This can be harnessed to rapidly manufacture polymer films possessing prescribed height profiles. To quantify and verify this phenomenon, a model is described here which accurately predicts the formation, growth, and eventual dissipation of topographical features. The model predictions, based on numerical solutions of equations governing thin film dynamics with a Marangoni stress, are quantitatively compared to experimental measurements of thin polystyrene films containing photochemically patterned surface energy gradients. Good agreement between the model and the data is achieved at temperatures between 120 and 140 °C for a comprehensive range of heating times using reasonable physical properties as parameter inputs. For example, thickness variations that measure 102% of the starting film thickness are achieved in only 12 minutes of heating at 140 °C, values that are predicted by the model are within 6% and 3 min, respectively. The photochemical pattern that directed this flow possessed only a 0.2 dyne cm(-1) variation in surface tension between exposed and unexposed regions. The physical insights from the validated model suggest promising strategies to maximize the aspect ratio of the topographical features and minimize the processing time necessary to develop them.