The interactions of block copolymers with surfaces can be controlled by coating those surfaces with appropriate statistical copolymers. Usually, a statistical copolymer comprised of monomer units identical to those of the block copolymer is used; that is, typically a poly(styrene)-stat-poly(methyl methacrylate) (PS-stat-PMMA) is used to direct the alignment of poly(styrene)-block-poly(methyl methacrylate) (PS-block-PMMA), and poly(styrene)-stat-poly(2-vinylpyridine) (PS-stat-P2VP) has been used for poly(styrene)-block-poly(2-vinylpyridine) (PS-block-P2VP). Reports of controlling the orientation of block copolymers with statistical copolymers with a dissimilar composition are limited. Here, we demonstrate that this method can be further extended to show that PS-stat-PMMA can be used to control the wetting properties of poly(styrene)-block-poly(D,L-lactide) (PS-block-PDLA). Surfaces were modified with a series of cross-linked PS-stat-PMMA-stat-glycidyl methacrylate terpolymers, and the surface chemistries and energies were assessed using angle-dependent X-ray photoelectron spectroscopy and the two-liquid harmonic method, respectively. From these experiments, an expected neutral compositional window was identified for symmetrical PS-block-PDLA. Moreover, high-resolution SEM, AD-XPS, and grazing-incidence SAXS measurements were used to evaluate the morphology of PS-block-PDLA as a function of the surface composition of the underlying cross-linked copolymer films, and the neutral composition was found to range from 32 to 38 mol % of PS, in the bulk polymer. Ultimately, we demonstrated the determination of nonpreferential surface compositions that allow the self-assembly of lamellae with sizes in the sub-10 nm regime that are oriented perpendicular to the substrate. These findings have important implications for the use of PS-block-PDLA block copolymers in directed self-assembly, most specifically in advanced lithographic processes.

A series of high-performance polycarbonates have been prepared with glass-transition temperatures and decomposition temperatures that are tunable by varying the repeat-unit chemical structure. Patterning of the polymers with extreme UV lithography has been achieved by taking advantage of direct photoinduced chain scission of the polymer chains, which results in a molecular-weight based solubility switch. After selective development of the irradiated regions of the polymers, feature sizes as small as 28.6 nm have been printed and the importance of resist-developer interactions for maximizing image quality has been demonstrated.

Directed self-assembly of block copolymers (BCPs) is a promising technique for the nanofabrication of structures with dimensions smaller than what can be achieved by current photolithography approaches. In particular, there has been significant interest in the development of BCPs that can achieve ever smaller feature sizes with low levels of defects. Here we investigate the directed self-assembly of a high-χ BCP, polystyrene-block-poly(DL-lactide), which is capable of producing structures with dimensions less than 10 nm. In addition, we study the behavior of the BCP under nanoconfinement and the ability of the polymer chains to compress and stretch in response to the geometry of the confining volume. Key findings of this study are that the level of defects in the self-assembled structures are strongly related to the relative interfacial interactions of the BCP as well as the degree of frustration of the polymer chains under nanoconfinement relative to the bulk. These results have particular significance for nanofabrication of ordered structures, which is of relevance for the fabrication of nanowires, metamaterials, and next-generation computer chips.

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Three strategies for approaching the design and synthesis of non-chemically amplified resists (non-CARs) are presented. These are linear polycarbonates, star polyester-blk-poly(methyl methacrylate) and comb polymers with polysulfone backbones. The linear polycarbonates were designed to cleave when irradiated with 92 eV photons and high T g alicyclic groups were incorporated into the backbone to increase T g and etch resistance. The star block copolymers were designed to have a core that is sensitive to 92 eV photons and arms that have the potential to provide properties such as high T g and etch resistance. Similarly the polysulfone comb polymers were designed to have an easily degradable polymer backbone and comb-arms that impart favorable physical properties. Initial patterning results are presented for a number of the systems.