The need to overcome feature-size limitations in conventional photolithography has led to interest in block copolymer (BCP) systems, which can produce features on the 1-100nm length scale. 1 BCPs that incorporate an inorganic moiety, such as silicon, into one of the blocks are attractive because they frequently exhibit high χ- parameters2-4 and form a robust oxide mask after reactive ion etching, improving etch contrast 5 . The present paper describes the synthesis and self-assembly of block copolymers composed of naturally-derived oligosaccharides coupled to a silicon-containing polystyrene derivative synthesized by ARGET ATRP. The block copolymers exhibit large χ enabling formation of 5 nm feature diameters, silicon incorporation in one block for oxygen reactive ion etch resistance, and bulk and thin film self-assembly into hexagonally packed cylinders facilitated by a combination of spin-coating and solvent annealing techniques. As observed by SAXS and AFM, these materials exhibit some of the smallest block copolymer features in the bulk and in thin films reported to date.
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